Chemical products and their preparation



United States Patent 3,390,966 CHEMICAL PRODUCTS AND THEIR PREPARATION Walter H. Knoth, Jr., Mendenhall, Pa., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 135,710, Aug. 24, 1961. This application Nov. 13, 1962, Ser. No. 237,392

29 Claims. (Cl. 23-361) This application is a continuation-in-part of my copending application Ser. No. 135,710, filed Aug. 24, 1961, now abandoned, which in turn, is a continuation-in-part of my application Ser. No. 6,852, filed Feb. 5, 1960, and now abandoned.

This invention relates to new boron compounds. More particularly, it relates to a new class of ionic boron compounds and to their preparation.

Boron compounds, particularly boron hydrides, have achieved technical importance in recent years. In many potential applications boron compounds, including boron hydrides, halides and alkyls, have been severely limited by hydrolytic, oxidative and other types of instability. To illustrate, diborane, chlorodiborane, pentaborane and trialkylboron compounds are spontaneously flammable in air. Diborane, pentaborane, chlorodiborane, boron trichloride, iododecaborane and most other boron halides are rapidly hydrolyzed in water or alcohol. Even the most stable known boron hydride, i.e., decaborane, is hydrolyzed at a moderate rate in water. Ionic boron hydrides, e.g., sodium borohydride and sodium deca'borohydride, are similarly hydrolyzed at a rapid rate at 100 C.

This invention is directed to a broad class of boron compounds which have stability characteristics that are unique among boron compounds. The compounds of the invention generally show hydrolytic, oxidative and chemical stabilities normally associated with aromatic organic compounds.

The novel class of ionic boron compounds are represented generically by the following formula:

M is an atom or group of atoms which forms a cat?on, i.e., a positively charged ion, in aqueous solution; X represents a monovalent substituent capable of bonding to carbon of a benzene nucleus by replacement of hydrogen bonded to said carbon; y is a positive Whole number of 1-10, inclusive; and a and b are positive whole numbers of 1-3, inclusive, whose values are determined by the valence of M, i.e., a multiplied by the valence of M is equal to 2b. The X groups, when more than one is present, can be alike or ditferent.

In the compounds represented by generic Formula 1, the novel and characterizing component is the boron-containing group shown in parentheses, i.e., B H X This group forms an anion in aqueous solution and it behaves as a stable chemical entity or radical in conventional reactions. This group will be discussed more fully in later paragraphs with particular reference to the substituent X. Therefore the novel invention may be considered as comprising derivatives of the acid H B l-l and its salts, wherein at least one hydrogen of the 13 1-1 anion is replaced by an X substituent.

The group M In the generic formula, M is a group which can be composed of one or more than one element and which is ionically bonded to the boron-containing group. To illustrate, when M is a monovalent group, the compound can be represented by the following formula to show the ionically-bonded groups: (M+) (B H X When M 3,390,966 Patented July 2, 1968 is a divalent group, the compound is represented as follows: M++(B H X In like manner, when M is a trivalent group, the compound is repressented as follows: )2( 10 10-y y )3- The groups represented by M bear a positive ionic charge and they have in common the property of forming positively charged groups in water. The properties of these groups are not critical. The group M represents a broad range of elements and combinations of elements. To illustrate, M can be hydrogen, hydronium ('H O a metal, ammonium (NHJ), hydrazonium (NH NH N-substituted hydrazonium, aryldiazonium, sulfonium, phosphonium, metal ammine, long chain pyridinium, and the like.

To illustrate, M can be lithium, sodium, cesium, beryllium, barium, lanthanum, zirconium, vanadium, manganese, iron, cobalt, copper, zinc, mercury, aluminum,

thallium, tin, lead, antimony, bismuth, silver, or any other metal.

As further more specific examples, M can be RNH R NH R3NH+, R.,N+, (RNHNH (R NNH R S+, or R ,P+, where R is an organic radical bonded to the nitrogen, sulfur or phosphorus. The R groups are not critical features of these cation groups. The subs'tituents represented by R can be open-chain or closed-chain, saturated or unsaturated, or the groups can be composed of heterocyclic rings of which the nitrogen, sulfur, or phosphorus is a component, e.g., pyridine, quinoline, morpholine, hexamethyleneimine, and the like. Preferably R, for reasons of availability of reactants, represents a hydrocarbon group of at most 18 carbons.

The group M can be a Werner-type coordination complex, e.g., a metal ammine such as [Ni(Nl-I a)6] 2 2 4 2)a] 3)s] and the like.

The group (B l-I X The pertinent feature in the novel group is the substituent X, which is bonded to boron. The number of substituents which can be present in the group is not less than 1 or more than 10 and the substituents can be alike or different.

In its broadest aspects, X is a monovalent group which has the characterizing property of forming XC bonds where C represents a carbon which is a nuclear member of a benzene ring and where the XC bond is formed in place of the HC bon-d. The property of forming X- -C bonds, where C is nuclear carbon as defined above, is corrmiou to all the groups which are represented by X.

The group X can represent a substituent introduced into the B H anion by direct reaction or it can represent a substituent obtained by subsequent chemical modification of a group which has been introduced by direct reaction, e.g., a substituent obtained by reduction, esterification, hydrolysis or amidation of directly introduced groups.

The ionic charge of 2 on the boron-containing anion refers to a charge which is inherent in the boro-hydrogen cage structure. The value of the ionic charge is independent of and does not take into consideration any ionic charge which may reside in the X substituents by virtue of ionizable functional groups. The ions which are formed by ionizable substituents are considered to be part of the X groups and are included Within the definition of these groups. For example, carboxyl, sulfo, amino and like substituents will function as groupswhich possess acidic or basic properties which are independent of the properties of the boron cage structure.

Compounds of the invention are obtained by processes which employ as a principal reactant a salt or acid having the B H anion. 'In one process, substituents are intro duced directly into the B H f anion by reaction with an electrophilic reagent. Su-bstituents Obtained by this process are called herein-after electrophilic groups and these groups form a preferred class of substituents. Thus, in this preferred group, X is a monovalent group which is capable of bonding to carbon of a benzene nucleus by reaction of benzene or a substituted benzene with an electrophilic reagent.

Arr electrophilic group is a group which is deficient in electrons and which has a point of low electron density. Electrophilic groups and reagents which are employed to effect substitution of such groups for hydrogen on carbon of a benzene nucleus are described in conventional textbooks, of which the following are examples:

Examples of electrophilic groups or substituents which are included in the scope of X are as follows: halogens (F, Cl, Br, I), hydrocarbon R'),

H H carboxyl (C-OH), N, N-disubstituted carbamyl (C-NR'z) halotormyl (t'i-Y, where Y is F, Cl, Br, I)

cyano (CN), trihalomethyl (CCI -CF etc.),

nitro (NO nitroso (-NO), hydrocarbylazo (-N=NR') sulfo SO H), sulfonyl (SO R'), and mercuric acetyl ll (HgOCCHa) R' where used in the above substituents is a monovalent organic group which is preferably a hydrocarbon group (alkyl, cycloalkyl, a'lkenyl, cycloalkenyl, aryl, alkaryl, aralkyl) of at most 18 carbons.

A second and larger preferred group of compounds of the invention includes those in which X can be introduced directly into the B H f' anion, not necessarily by electrophilic attack, or the group can be obtained by modification of an X substituent present on the anion. Examples of substituents which are included within the scope of X in this preferred group are as follows: halogens (F, Cl, Br, I), hydrocarbon, carboxyl i (COH) carbamyl and N-substituted carbamyl i l? t? (CNHz, -CNHR), -GNR), halocarbonyl (C-Y where Y is F, Cl, Br, I)

halomethyl -(--OH Y', where Y is F, Cl, Br, 1), hydroxyl (OH), hydrocarbonoxy (OR'), monooxahydrocarcycloalkenyl, aryl, alkaryl, aralkyl, and the like) of at most 1'8 carbons.

The number of substituents Which can be present on the decahydrodecaborate(2 anion is not less than 1 or more than 10. Thus, the anion (B H X in the generic formula, ('M),,'(B H X may range from (B 'H X) through successively decreasing hydrogen content to (B X Examples of the new compounds of the invention, illustrated by formulas are as follows:

O I N33 B mHKHgO (ii 0 H3) a 3 2B10H8 slz and 4 9 4 2B10H9OCH2CH2OCH3 The scope of the monovalent groups encompassed by X in the generic formula for the compounds of the invention can be understood more clearly by describing methods for obtaining the compounds.

Preparation of compounds Electrophilic substitution-In this method, which involves the direct substitution of hydrogen, two reactants are employed which are defined as follows:

(a) A boron-containing compound of the general formula M (B H wherein M, a and b have the meanings given earlier in generic Formula 1 for the novel compounds.

(b) A reagent capable of introducing an electrophilic group into a benzene nucleus by replacement of hydrogen bonded to a carbon of said nucleus. This second reactant is referred to as an electrophilic reagent.

The characteristics of each group of reactants are discussed in more detail in the following paragraphs.

The boron-containing reactant, M (B H is a dibasic acid or a salt of a dibasic acid which has, as a characterizing group, a divalent anion, (3 1-1 0 This anion will be referred to as the decahydrodecaborate(2.) anion or, for simplicity, as decahydrodecarborate (2-) At this point, it should be noted that the novelty of the compounds of the invention is such that no officially approved system of nomenclature has yet been established. The name decahydrodecaborate(2) follows the lines recommended for naming other boron compounds and its use here permits the logical naming of a derivative of the (B H anion as a substituted decaborate (2) Decahydrodecaboratefi is a unique species of divalent anion which has remarkable and unexpected chemical properties. In many respects it shows much greater chemical stability than any previously reported boron hydride, whether neutral or bearing a charge. For example, the anion is inert to sodium methoxide in refiuxing methanol and it does not hydrolyze in water. The anion forms salts with basic materials, e.g., amines and metals, and from these salts there can be obtained a strongly acidic hydronium compound by treatment with an ion exchange resin. Solutions of silver nitrate are not reduced by aqueous solutions containing the B I-I anion, a behavior which is in marked contrast to the behavior of other boron hydrides.

It is surprising, in view of the chemical stability described above, to find that the decahydrodecaboratefl anion undergoes electrophilic substitution reactions in a manner which resembles the behavior of a carbocyclic aromatic compound, e.g., benzene or naphthalene. More specifically, the hydrogens bonded to boron in the B H group are replaceable by substituents which can also replace hydrogen bonded to nuclear carbon in benzene or a substituted benzene such as toluene. This behavior of the decahydrodecaborate(2) anion is particularly surprising in view of the completely inorganic composition of the anion. It is the previously unknown aromatic character of the decahydrodecaborate(2-) anion which forms the basis of the present invention leading to a broad range of novel substituted decaborates (2.)

It is evident from the above description of the chemistry of the decahydrodecaborate(2-) anion that the second reactant, i.e., the electrophilic reagent, employed in preparing the novel compounds is a reagent which can effect a substitution reaction on a benzene nucleus. These reagents, in view of the extensive work which has been done on substitution reactions in the benzene nucleus, form a well-known group of compounds.

Electrophilic reagents which are broadly operable in the process are reagents which will effect direct substitution of hydrogen bonded to carbon of a benzene nucleus, i.e., the hydrogen is replaced by a group derived from the electrophilic reagent. Electrophilic reagents are compounds which react by acquiring electrons or acquiring a share in electrons which previously belonged to a foreign molecule (see Ingold, vide supra, p. 201). Examples of electrophilic reagents which are within the scope of the above definition and which are operable in the process of the invention are given below, together with the substituent group which in the process is bonded to boron in the final product.

Electrophilic Reagent Electrophilic Group Bonded to Boron Halogens (F Cl Brz, I2) Halogen (F, Cl, Br, I) Cyanogen halides (CNF, CNCl)... Nitrile (ON) Sulfuric acid -SO H Nitric acid. NO3 HgNOSO3H" -NH Olefins alkyl {e.g., -C H5, CH(CH3):] Acetylenes alkenyl |0I Aeyl halides C-R II 0 Hg(OCOH;)1 -HgOOCH (OH)2C=C(CN) (CN)C=C(ON): HN Oz -NO (H) CO/HCl -CH R'SOzCl -SOz-R" I t RWNCCI CNR;" (R '0 R"'-H)+Cl- (oxonium salt) --O R (ROHz)+Cl- (oxonium salt) (H3O)+C1" (hydronium salt). RSCl In the above groups, R" is a monovalent organic radical, preferably hydrocarbon of at most 18 carbons, which can be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, and the like. I

In the reactions employing some of the above electrophilic reagents, a catalyst may be used, e.g., aluminum trichloride, boron trifiuoride and polyphosphoric acid. These catalysts are employed in the same manner as in the wellknown procedures in organic chemistry. In some cases the boron compounds themselves function as catalysts, e.g., in alkylation of (H O) B H The electrophilic reagents employed in the process are materials which are usually readily available or which are obtained by conventional methods.

Processes which are employed to introduce one or more X groups on the boron cage are not necessarily identical with the processes employed to introduce the X groups on a benzene nucleus. Consideration must be given to differences in reactivity or in reaction mechanism between a completely inorganic system, as represented by the B H anion, and an organic aromatic system represented by the benzene ring. The differences in preparative procedures which may be employed do not change in any way the common characteristic or property of all of the X groups, i.e., the property of bonding to a nuclear carbon of a benzene ring.

It is surprising that, despite the inorganic nature of the boron-containing reactant, so many of the processes employed in aromatic chemistry are, in fact, operable in the present invention, e.g., the processes of halogenation, alkylation, acylation, amination, and the like. Even more surprising and unexpected is the fact that the X groups bonded to boron in the decaborate(2) anion exhibit a chemical behavior in subsequent reactions which resembles closely the behavior of the same X groups bonded to an aromatic nuclear carbon. This similarity in behavior permits the preparation of a broad range of X substituents bonded to the boron cage.

In view of the above discussion, it is obvious that a wide range of processes is available for the preparation of compounds of the invention. These processes are illustrated more fully in the examples which appear later.

In the preparation of the compounds of the invention by the process described above, the substitutent which ultimately is bonded to boron in the final product is not necessarily the substituent which would be obtained with a process employing a conventional carbocyclic aromatic reactant. T 0 illustrate, reaction of formaldehyde with a decahydrodecaborate yields a compound of Formula 1 in which X is -OCH instead of --CH OH which might be obtained. Variations of this nature from conventional results are not unexpected in view of the completely inorganic character of the decahydrodecaborate reactant. Such variations do not change the view of the basic aromatic character of the boron sphere or cage in the decaborate anion.

The boron hydride reactants of the formula are materials which can be obtained by relatively simple methods from a decaborane(12)/organic sulfide adduct of the general formula B H -ZZYSY', where Y and Y are hydrocarbon groups, preferably alkyl. The adduct is pre-.

pared by reacting an organic sulfide of the formula YSY' with decaborane( 14), i.e., B H at a temperature between and 150 C. until approximately 1 mole of hydrogen is evolved. The decaborane(12)/organic sulfide adduct is then reacted with liquid ammonia or an amine at a temperature between about 50 C. and 0 C. for about 1 hour to obtain the salt M (B H where M represents the cation derived from ammonia or the amine. Thus, with liquid ammonia as the reagent, M is (NH with methylamine, M is (CH NH and with ten.- butylamine, M is [(CH CNH Reaction of the decahydrodecaborate(2.) salts to obtain the compounds of the invention is conducted in conventional vessels with corrosion-resistant inner surfaces, e.g., glass, platinum, poly(tetrafluoroethylene)resin, and the like. The decahydrodecaborate salt, Ma(B H and, optionally, an inert liquid solvent is charged into the reaction vessel. The electrophilic reactant is then supplied to the reaction vessel at a temperature and at a rate which will provide a controllable reaction and which will bring the reaction to completion within a reasonable time. When electrophilic reagents are employed which are hydrolytically stable, water or alcohols (methanol, ethanol) can be used conveniently as a solvent for the reaction. Other solvents can be used, for example, diethyl ether, benzene, heptane, carbon tetrachloride, carbon disulfide, and the like.

The temperature at which the reaction is conducted will be determined largely by the reactivity of the electrophilic reagent. In general, the temperature will be between about -20 C. and 150 C. Preferably, the temperature will be between about 0 and about 100 C.

The time of reaction in a batch process will also depend to a considerable extent on the reactivity of the electrophilic reagent. The reaction generally proceeds rapidly and, with thorough mixing of the reactants, the time may be as low as 5 minutes or even less. Generally a reaction time between about minutes and 5 hours is sufiicient. It is desirable and advantageous to mix the reactants by any suitable means although mixing is not essential for operability. In some cases, e.g., with alkyl halides as the electrophilic reagent, catalysts are used in the process employing the technology of well-known organic aromatic chemistry.

The reaction can be conducted under pressure, if desired, but it is not essential to use pressure. In most cases, the reaction proceeds satisfactorily at atmospheric pressure.

The proportions in which the reactants are used are not critical. It is preferable, in order to obtain maxi-mum yield of desired product, to use at least one mole of the electrophilic reagent for each hydrogen which is to be replaced on the decaborate (2r) anion. It is not essential, however, that these ratios be used.

The compounds are purified by well-known and recognized procedures. For stable products, conventional crystallization procedures are used, employing water or alcohol as solvents. For products of limited stability, solutions of the products can be treated with absorptive agents, e.g., activated carbon or silica gel, to adsorb the major portion of the impurities.

Indirect substitution.-A second process for obtaining compounds of the invention in which X is hydroxyl,

amine or substituted amine, is conducted in two steps. The reactants in the process are (1) a decahydrodecaborate(2-), described in the previous process, and (2) an amide derived from a carboxylic acid. In the initial step in the reaction an intermediate product can be obtained which, particularly in the preparation of products bearing OH groups, is isolated and used in a second stage in the process. The intermediate reactant thus obtained can be a non-ionic compound of the formula B H '2Z or an ionic-type compound of the formula M(B H 'Z) where Z is an amide of a carboxylic acid, M has the meaning given in Formula 1 and b is a number which is equal to the chemical valence of M. These prodducts are new and their preparation is described more fully in the following paragraphs.

The intermediate products described above are not isolated in processes to obtain compounds bearing NR substituents.

The amide and a decahydrodecaborate salt, e.g., (NI-IQ B H or Na B H are mixed to form a solution, and a hydrogen halide, e.g., hydrogen chloride, is bubbled through the mixture. The reaction is exothermic and proceeds rapidly. To obtain the non-ionic species as the principal product, heat is applied to the reaction mixture after the exothermic phase has passed and passage of the hydrogen halide is continued for a further period. To obtain the ionic species as the principal product, passage of hydrogen halide is stopped when the exothermic phase is over, as evidenced by a drop in temperature and no further heat is applied. In either case the reaction mixture is processed by filtration. The filtrate is diluted with Water and the non-ionic species whi h is insoluble is separated. The remaining clear solution is reacted with a solution of a compound which contains the cation M, desired in the final product. Thus, the solution can be reacted with an inorganic base, an organic base, an inorganic salt, an organic salt, and the like. To illustrate, the solution can be reacted With NaOH, CsOH, Ba(O-H) NH NH OH, substituted amines, tetrasubstituted nitrogen bases, and the like, to obtain compounds in which M covers a broad range of cations. Salts which can be used as reactants are, e.g., chlorides, carbonates, acetates of metals or organic bases of the kind illustrated above. This step in the process is a simple metathetic reaction and its many variations are wellknown in chemical processes.

The preferred amides for use in the process are formamides, acetamides and N-substituted-Z-pyrollidones in which the nitrogen, preferably, bears hydrocarbon substituents, i.e., compounds of the formula aqueous solution of a strong base, e.g., an alkali metal hydroxide, and the mixture is warmed for a time sufiicient to hydrolyze the amide portion of the adduct. A reactant with the desired cation, i.e., M group, is added to the mixture to precipitate the boron compound as a salt of the general formula M,,[B I-I (OH) where M, a, b, and y have the meanings given for Formula 1.

Compounds of Formula 1 in which X is amine or a substituted amine group are prepared most readily by mixing the acid, (H O) B H and an amide in aqueous solution. The solution is heated until water is removed completely and it is then refluxed. Dilution of the solution with an alcohol, e.-g., CH OH, followed by addition of a salt having an appropriate cation leads to the isolation of a compound of generic Formula 1 in Which X is NH NHR' or NR A second group of products is obtained in this reaction which are compounds of Formula 1 in which X is formyloxy or hydrocarbonyloxy, i.e., OC(O)H or To illustrate, with dimethylformamide as the reactant, compounds of Formula 1 are obtained in which X is OC(O)H; with dimethylacetamide, compounds in which X is -OC(O)CH are obtained. This group of compounds are also obtained readily by esterification of the hydroxyl-bearing compounds as described below.

The hydroxyland amine-substituted compounds can be used as intermediates for the preparation of compounds of the invention in which X is bonded to boron through oxygen or nitrogen. To illustrate, the hydroxyl-bearing compound is reacted with acids, acid halides or acid anhydrides to obtain compounds in which X represents an ester group [OC(O)R', or OC(O)H]; with isocyanates to obtain compounds in which X is RNHC(O)O-; with olefins to obtain compounds in which X is OR'; with acetylenic compounds to obtain products in which X is OCI-I=CHR'; with sulfonyl halides to obtain products in which X is OSO R', and the like. As a further illustration, the amine-bearing compounds can be acylated to give products having groups such as NHC(O)R' and they can be reacted with isocyanates to obtain compounds having groups such as NHC(O)NHR'.

In the above description, R has the meaning defined in an earlier paragraph.

X groups which are not alike.-The processes which have been described can be employed to obtain compounds having one or more X groups. These groups, if more than one is present, can be alike or different. To obtain compounds having two or more X groups which are unlike, the decahydrodecaborate is reacted with one electrophilic reagent until the desired number of substituents are introduced and the partially substituted product is then reacted with a second electrophilic reagent. The intermediate partially substituted product can, if desired, be isolated prior to reaction with the second electrophilic reagent. The process can be repeated with a third electrophilic reagent, or even further, until all hydrogens bonded to borons have been replaced. Further modification of various substituent groups can be accomplished by conventional methods to obtain compounds having a broad range of X groups.

To illustrate, compounds of the following formulas can be obtained by the methods described above:

In the processes described above, direct replacement of hydrogen bonded to boron by another element or group of elements can occur, i.e., substitution, or the substituent atom or group can be replaced wholly or in part by some other atom or group, i.e., displacement. Whether the reaction is substitution, replacement or displacement, there is no change in the geometry of the decaborate cage or decaborate moiety. ,1

The new compounds are usually solid products which are salt-like in character. Many of the compounds dissolve in water. The color of the compounds is dependent to some extent on the nature of the electrophilic group bonded to boron. Thus, chlorine and bromine substituted compounds are generally colorless products while nitro and nitroso-substituted derivatives are highly colored. The compounds vary in stability and caution must be exercised in handling them. Nitro and nitroso-substituted derivatives may in some cases be highly sensitive to shock and they are preferably kept moist while handling. Other derivatives, e.g., the halogen-substituted products, the alkyl-substituted compounds or those bearing acyl groups, are stable and they can be kept in storage for prolonged periods in conventional containers.

The products of the invention and processes for obtaining them are illustrated in the following examples. The preparation of a representative compound of the type M,,( B H which is employed as a principal reactant, is also illustrated. Processes are described in the examples which are specific for the preparation of compounds having a particular group of substituents, e.g., hydrocarbon mercapto groups (SR').

EXAMPLE A (A) Preparation of a decaboryl bis(dialkyl sulfide).- A reaction vessel having a capacity of about 365 g. of water is charged with 0.79 g. of decaborane(l4), cooled in liquid nitrogen, and then evacuated to a pressure of 10 microns of mercury. Approximately 21 g. of methyl sulfide is condensed onto the decaborane in the reaction vessel. The reaction vessel is closed, allowed to warm to room temperature and stand for 4 days. During this time, 6.6 millimoles of hydrogen is evolved. The reaction vessel is opened and excess methyl sulfide is removed by distillation, leaving a practically quantitative yield of white solid residue of B H -2(CH S. The compound is recrystallized from ethyl acetate and it melts at 122- 124 C. The compound is called bis(-dimethyl sulfide)decaborane( l2) The above procedure is equally operable with other organic sulfides.

(B) Preparation of M B H (where M is NH Bis'(dirnethyl sulfide)decaborane(12) (8.5 g.) is mixed with 50 ml. of liquid ammonia and stirred in a roundbottom reaction vessel for 1 hour with the vessel being cooled to a temperature of about 50" C. by partial immersion in a bath of a mixture of solid carbon dioxide and acetone. The cooling bath is then removed and the excess ammonia is allowed to evaporate with stirring. The remaining traces of ammonia are removed by subjecting the residue to a high vacuum (0.01 mm. of mercury) at 25 C. There is obtained 5.6 g. of solid residue which is virtually a quantitative yield of diammonium decahydrodecaborate(2-), i.e., (NH4)2B10H10.

By substituting other amine bases for liquid ammonia in the process of Part B, a Wide range of substituted ammonium derivatives is obtained, e.g., trimethylamine yields [(CH NH] B ,H isopropylamine yields Similarly, tert-butylamine yields [(cH hCNH hB l-l and butylamine yields (C H NH B H (C) Preparation of H B H nH O or A solution of (NHQ B H obtained in part B, in 30 ml. of water is passed through a 0.5" diameter chromatography column containing ml. of a commercial acidic ion exchange resin (Amberlite IR -H). The water eiiiuent is clear, colorless and acidic. The column is rinsed with more water until the efiluent is no longer acidic and the water fractions are combined. Evaporation of the combined aqueous solutions under reduced pressure (1 mm. mercury) at a temperature of about 40 C. leaves a yellow viscous liquid which is H B H -(H O) The compound can also be written as 3 2 10 1o 2 It is neutralized with (CH NOH to yield Qtt h m m 11 with isopropylamine to yield (C H NH B H EXAMPLE 1 A reaction vessel, equipped with a stirrer and means for cooling, is charged with 2.0 g. of diammonium decahydrodecaborate(2'"), (NHQ B H and 40 ml. of water. The solution is cooled to ice-water temperature and chlorine gas is bubbled through it. The solution is stirred during the reaction which is exothermic. The addition of chlorine gas is continued until the exothermic reaction subsides. An aqueous solution of 5.5 g. of tetramethylammonium chloride is added carefully and a white solid forms. The solid is separated by filtration and it is purified by crystallization from water. There is obtained 4.65 g. of bis(tetramethylammonium) octachlorodihydrodecaborate(2") as white needle-shaped crystals. The compound has the formula [(CH3)4N]2B10H2C18. It does not react with silver nitrate in boiling water.

Analysis.Calcd for C H B Cl N C, 17.7; H, 4.8; B, 19.99; Cl, 52.4; N, 5.11. Found: C, 17.38; H, 5.06; B, 19.56; Cl, 52.85; N, 4.46.

EXAMPLE 2 (A) A reaction vessel, equipped with a stirrer, is charged with 120 ml. of water and 8.0 g. of

Vessel and contents are cooled to 10-15 C. and chlorine gas is passed through the aqueous solution until no rise in temperature above about 25 C. occurs when the vessel is'removed from the cooling mixture.

A portion of the reaction mixture is removed and it is mixed with an aqueous solution of cesium chloride. The white precipitate which forms is separated by filtration and it is washed thoroughly with water. The product is dicesium ctachlorodihydrodecaborate(2*), i.e., Cs B fl Cl whose identity is confirmed by its infrared absorption spectrum. It is obtained in colorless needle-like crystals by crystallization from water.

Chlorination of the mixture which is left in the reaction vessel is continued for 1 hour at about 25 C. A transient dark violet color forms in the mixture which fades after chlorination is stopped. A saturated solution of 21 g. of CsCl in water is added with stirring to the mixture and the white precipitate which forms is separated by filtration. The product is recrystallized from water to obtain 22 g. of dicesium decachlorodecaborate (2*) as needle-like crystals. The identity of the compound, which has the formula Cs B Cl is confirmed by elemental analysis.

Analysis.-Calcd for Cs B CI B, 14.8; Cs, 36.5; C1, 48.7. Found: B, 14.7; Cs, 34.0; Cl, 48.23.

(B) A reaction vessel is charged with 125 ml. of water and 5.0 g. of (NHQ B H The mixture is stirred and cooled to 515 C. Chlorine gas is bubbled through the mixture until the exothermic reaction ends. At this point passage of chlorine gas is stopped and nitrogen is bubbled through the mixture for 5 minutes to remove excess chlorine. The mixture is allowed to warm to about 25 C. and an aqueous solution of cesium chloride is added with stirring until precipitation of a white solid is complete. The mixture is partially evaporated by warming and the solid is separated by filtration. There is obtained 17.7 g. of Cs B H Cl which is purified by recrystallization from water.

Analysis.--Calcd for Cs B H Cl Cs, 40.3; B, 16.4; C1, 43.0. Found: Cs, 38.9; B, 15.56; Cl, 44.25.

The compound is soluble in cold 1,2-dimethoxyethane but, on boiling, it separates as an insoluble liquid which redissolves on cooling.

The free acid, H B H Cl is prepared in aqueous solution by passing an aqueous solution of Cs B H Cl through a column packed with a commercial acidic ionexchange resin. The silver salt, Ag B H Cl is obtained by reacting an aqueous solution of the above acid with silver oxide. The silver salt is soluble in water.

(C) A reaction vessel is charged with ml. of water and 6.0 g. of (NH B H Chlorine gas is bubbled through the mixture at 10-15 C. until the exothermic reaction subsides. The solution turns blue near the beginning of the reaction and the color persists. After passage of chlorine is stopped, a stream of nitrogen is passed into the mixture and it is permitted to come to room temperature (about 25 C.) After standing overnight the solution is still blue in color. An aqueous solution of CsOH is added to the mixture until it is slightly basic. The solution is filtered and the filtrate is evaporated. The solid product is recrystallized from water until it is free of chloride ion (as shown by test with aqueous AgNO There is obtained 15.5 g. of Cs B H Cl -H O. The compound is identified by elemental analysis.

Analysis.Calcd for Cs B H Cl -H O: B, 15.9; C1, 41.9. Found: B, 16.36; Cl, 41.44.

(D) An aqueous solution of Cs B cl is prepared by heating 9.6 g. of the cesium salt with ml. of water. The solution is passed through a column packed with an acidic ion-exchange resin (Amberlite IR- 120H) to obtain an aqueous solution of the acid H B Cl The aqueous acid solution is treated with freshly prepared Ag O until no further reaction with the oxide is noted. The solution is filtered and the filtrate is evaporated to give about 4.0 g. of a white crystalline solid which is AggB oclm. The identity of the compound, which is free of Water of hydration, is confirmed by its infrared absorption spectrum.

The above process is repeated employing 15 g. of Cs B Cl as the reactant in aqueous solution. The identity of the silver salt which is obtained is confirmed by elemental analysis.

Analysis.-Calcd for Ag B Cl Ag, 31.8; B, 15.9. Found: Ag, 31.58; B, 16.98.

(E) An aqueous solution containing 50 g. of cs B Cl is passed through an acidic ion-exchange column of the type described in Part D. The acid efiiuent is reacted with barium carbonate until the solution is neutral. The mixture is filtered and the filtrate is evaporated to dryness to yield BaB Cl as a white, crystalline very hygroscopic solid.

The preparation is repeated and the white crystalline compound is recrystallized from water. It is dried for about 18 hours under reduced pressure to yield a hydrated BaB Cl The elemental analysis is as follows: Ba, 17.51; B, 17.96; Cl, 59.12.

(F) An aqueous solution containing 10 g. of Cs B Cl is passed through an acidic ion-exchange column of the type described in part D. The acid effluent is evaporated under reduced pressure to dryness, leaving a white, hygroscopic crystalline solid which is H B Cl containing six moles of Water of hydration [B, calcd., 18.88; B (found), 18.58].

The above process is repeated, employing an aqueous solution containing 30 g. of Cs B CI The solid product obtained by evaporation of the acid efiiuent is dried further in an Abderhalden unit under reduced pressure for 6 hours, employing refluxing alcohol to control the temperature. There is obtained 20.5 g. of H B Cl -6H O, also written as (H O) B Cl -4H O.

A nalysis.-Calcd for H B Cl -6H O: B, 18.88; CI, 62. 0. Found: B, 19.38; Cl, 61.76.

A portion of the hydrate of H B Cl is dried in an Abderhalden unit for 3 hours under reduced pressure at the boiling point of acetone. The acid thus obtained is a very strong acid and it contains 5 moles of water of hydration of which 2 moles are considered to be associated with the protons.

Analysis.-Calcd for (H O) B Cl -3H O: B, 19.5; C1, 64.1; NE, 277. Found: B, 19.91, 20.04; Cl, 63.04, 6299; NE. 271.

A second portion of the hydrate of H B CI is added to a solution consisting of equal volumes of concentrated hydrochloric acid and dimethyl sulfoxide. The solid which precipitates is separated by filtration and it is crystallized from water. The product which is obtained is H B Cl containing dimethyl sulfoxide as solvent of crystallization.

Analysis.-Calcd for H B Cl -4(CH SO: C, 12.35; H, 3.48; Cl, 45.6; B, 13.9; S, 16.4. Found: C, 12.60; H, 3.55; CI, 44.44; B, 14.7; S, 16.73.

A third portion of the hydrate of H B Cl is added to a solution of equal volumes of concentrated hydrochloric acid and dimethyltormamide. The solid which precipitates is separated and it is crystallized from water to obtain H B Cl containing dimethylformamide as solvent of crystallization.

Analysis.alcd for H B Cl -4HC(O)N(CH B, 14.3; N, 7.4; C, 19.0; H, 4.0. Found: B, 14.63; N, 7.28; C, 19.4; H, 4.1.

(G) A column is charged with an acidic ion-exchange resin of the type described in Part D. An aqueous solution of LiCl is passed through the column followed by an aqueous solution of LiOH to convert the ion-exchange resin to a lithium salt. An aqueous solution containing 7.6 g. Of HgBmClm [also referred to as (H3O)2B10C110], Obtained as described in Part F, is then passed through the column and the effluent is collected. The efiluent is evaporated under reduced pressure at 100 C. to dryness. The solid is dried further in an Aberhalden unit under reduced pressure for 6 hours, employing refluxing ethyl alcohol to control the temperature. There is obtained 5.8 g. of Li B Cl as a hydrated white crystalline product. The identity of the compound is confirmed by elemental analysis.

' Analysis.-Calcd for Li B Cl -'H O: Li, 2.45; B, 19.1; C1, 62.6. Found: Li, 2.3; B, 19.09; Cl, 62.77.

EXAMPLE 3 (A) A solution of bromine in water is carefully and slowly added with stirring to a solution of 0.22 g. of bis(tetramethylammonium) decahydrodecaborate(2-) in 30 ml. of water. The temperature of the reaction mixture is kept at 25 C. or lower during the addition. As soon as a solid precipitates, it is removed to prevent further bromination. The solid is dried as described in Example 1 and there is obtained 0.31 g. of bis(tetramethylamm'onium) pentabromopentahydrodecaborate(2-). The compound is a white crystalline solid which has the formula s)4 ]2 1o 5 5- (B) A solution is prepared which contains 5.0 g. of diammonium deoahydrodecaborate(2) in 50 m of methanol. The solution is stirred andthere is added to it over a period of minutes a solution of 3 g. of bromine in 50 ml. of methanol. The reaction mixture is filtered and the filtrate is evaporated under reduced pressure until all the solvent is removed. The white solid which remains is dissolved in water and to this solution there is added an excess of an aqueous solution of tetramethylammonium chloride. The solid which forms is separated by filtration. It is washed and dried to obtain 1.3 g. of his (tetramethylammonium) pentabromopentahydrodecabos)4 ]2 1o 5 '5- Analysis-Calcd for C H B Br N C, 14.5; H, 4.38; B, 16.35; Br, 60.55. Found: C, 13.75; H, 4.28; B, 15.95; Br, 60.88.

(C) To the aqueous filtrate remaining from the above preparation, there is added with stirring an aqueous solution of tetraethylammonium bromide. The solid which precipitates is separated and purified as described above. There is obtained 0.15 g. of bis(tetraethylammonium) tetra'bromohexahydrodecaborate(2),

46.2. Found: B, 16.26; Br, 48.43.

(D) A solution of 0.97 g. of bis(tert.-butyl-ammonium) decahydrodecaborate (2) (CH CNH B H is prepared in 30 ml. of water and the solution is filtered. The filtrate is charged into a reaction vessel immersed in a Water-ice bath. A mixture of bromine and water is added carefully and with stirring to the filtrate, care being taken to keep the temperature of the filtrate below 30 C. The addition of bromine and water is stopped when a brown color persists in the filtrate for about 1 minute. A solution of 2.8 g. of tetramethylammonium chloride in 10 ml. of water is then added carefully and with stirring. A white precipitate forms which is separated by filtration. The solid is Washed with water and it is dried about 18 hours at 50 C. under reduced pressure (about 1 mm. of mercury pressure). There is obtained 2.8 g. of bis(tetramethylammonium) heptabromotrihydrodecaborate(2). The compound is a white crystalline solid which has the formula [(CH3)4N]2B10H3BI'7. The excellent stability of the bromine boron bonds in the compound is shown by the fact that the compound is recovered unchanged after 1 hour in a refluxing methanol ml.) solution of sodium methoxide (0.46 g.).

Analysis.--Calcd for C H B Br N z C, 11.88; H, 3.33; B, 13.22; Br, 68.4; N, 3.92. Found: C, 11.60; H, 3.45; B, 12.17; Br. 68.93; N, 3.58.

(E) Di(propylammonium) decahydrodecaborate(2-) (2.0 g.) is dissolved in 50 ml. of ethanol and a solution of 10.6 g. of bromine in 41 ml. of ethanol is added dropwise with vigorous stirring of the decaborate solution. The bromine color disappears very slowly at the end of the addition. The reaction mixture is heated to reflux and a solution of 2.4 g. of bromine in 9 ml. of ethanol is added slowly.

The reaction mixture is divided into two equal parts. An excess of an alcohol solution of tetramethylammonium chloride is added to one part and a white solid precipitates. This solid is found to be a partia ly or incompletely brominated derivative.

The remaining portion of the reaction mixture is treated with a solution of 10 g. of bromine in 50 ml. of ethanol and the mixture is refluxed for 6 hours. The mixture is cooled and a solution of excess tetramethylammonium chloride in ethanol is added to it until precipitation of the white solid product which forms is completed. The white solid is separated by filtration, washed with ethanol and dried as described in Example 2. The white crystalline solid is his (tetramethylammonium) decabromodecaborate(2-), a compound which has the formula [(CH N] B Br The identity of the compound is confirmed by the infrared spectrum and by elemental analysis.

Analysis.-Ca1cd for C H B Br N C, 9.1; H, 2.29; B, 10.25; Br, 75.65. Found: C, 10.04; H, 2.90; B, 10.25; Br, 74.45.

(F) Diammonium decahydrodecabor-ate(2") (2.0 g.) is dissolved in 40 ml. of water and the solution is filtered. Bromine is added to the filtrate at ice-bath temperature with stirring until the bromine color persists. At this point, seven equivalents of bromine have been added. The solution is then concentrated under vacuum until ammonium bromide precipitates. The precipitate is removed by filtration, a large excess of ethyl acetate is added to the filtrate and the mixture is again filtered. The filtrate is concentrated under vacuum at about 40 C. until the color becomes dark red-brown. At this point the last traces of ammonium bromide are removed by filtration and the red-brown filtrate is concentrated to yield hydrated dihydrogen heptabromotrihydrodecaborate(2*), (H O) B H Br -nH O. The identity of the compound is confirmed by its infrared spectrum and by its conversion with tetramethylammonium chloride to bis- (tetramethylammonium) heptabromotrihydrodecaborate- (2), the same compound prepared in Part D.

(G) Bis(tetramethylammonium) decahydrodecaborate(2-) (1.5 g.) is dissolved in 30 ml. of water and bromine is added slowly with stirring in an ice-bath.

mohydrodecaborate(2 [(CH N] B HBr is obtained.

Analysis.-Calcd for C H B Br N B, 11.1; Br,

73.9. Found: B, 11.61; Br, 72.53.

EXAMPLE 4 (A) A reaction vessel, equipped with a stirrer and a reflux condenser, is charged with 6.0 g. of (NHQ B H and sufficient ethyl alcohol to form a clear solution. Excess liquid bromine is added and the mixture is stirred for 1530 minutes at prevailing atmospheric temperature (about 25 C.). The mixture is then heated to refluxing temperature and small portions are removed at intervals. Each portion is treated with an alcohol solution of (CH NCl to precipitate the tetramethylammonium decaborate. Refiuxing of the reaction mixture is continued until the infrared absorption spectrum determined on the test sample of the tetramethylammonium salt is free of B-H bands. At this point the reaction mixture is cooled and it is mixed with an alcohol solution of (CH ).;NCl. The precipitate which forms is separated by filtration. The product, which is [(CH N] B Br is purified by crystallization from a mixture of alcohol and acetone.

(B) The salt [(CH N] B Br obtained in Part A, is dissolved in about 4000 ml. of hot water and the solution is passed through a column packed with an acidic ion-exchange resin (Amberlite IR-12OH). Passage of the solution through the resin is repeated to assure complete removal of (CH N ions. The efiiuent is concentrated by warming to about 0.1 of its original volume. The liquid residue, which is an aqueous solution of H B Br is neutralized with an aqueous solution of CsOH. The neutralized solution is evaporated to obtain 14.3 g. of white crystalline dicesium decabromodecaborate (2), i.e., Cs B Br The identity of the compound is confirmed by its infrared absorption spectrum and by elemental analysis.

AnalySis.-Calcd for Cs B Br -H O: Cs, 22.3; B, 9.05; Br, 67.1. Found: Cs, 21.9; B, 8.99; Br, 66.89.

(C) A solution of 0.2 g. of Cs B Br -H O in ml. of water is mixed with a solution of 0.065 g. of AgNO in 5 ml. of water. The white precipitate which forms is separated by filtration to obtain silver decabromodecaborate(2-), i.e., Ag B Br The product, which is washed with water and ethanol to purify it further, becomes slightly brown on prolonged exposure to light and air.

Analysis.-Calcd for Ag B Br z Ag, 19.23. Found. Ag, 19.29.

(D) An aqueous solution containing 1.0 g. of Cs B Br is passed through a column packed with an acid ionexchange resin as described in Part B. The acid effluent, which contains H B Br is titrated carefully with a 0.1 N solution of NaOH and the titration curve is followed with a pH meter. The data show that the acid is very strong, comparable to inorganic mineral acids; the neutral equivalent is 591 (calcd, 596 for Cs B Br H2O The above process is repeated employing 10.5 g. of Cs B Br The neutralized acid eflluent (pl-i=7) is evaporated to dryness to obtain Na B Br as a white solid. The identity of the compound is confirmed by its Raman spectrum. Its identity is further confirmed by conversion to [(CH N] B ,Br obtained by reacting an aqueous solution of (CH NCl with an aqueous solution of Na B Br EXAMPLE 5 An aqueous solution of the acid prepared as described in Example 4, Part B, is added carefully and with stirring to an aqueous solution of cesium fluoride until precipi tion is complete. The precipitate is separated by filtration and it is crystallized from hot water to give a white crystalline product which is dicesium decabromodecaborate(2-), CSZBIDBI'IO.

Analysis.-Calcd for Cs B Br z B, 9.26. Found: B, 9.01.

EXAMFLE 6 A solution of 1.04 g. of diammonium decahydrodecaborate(2), (NHQ B H is prepared in 50 ml. of methanol and 5.6 g. of iodine is added carefully to the solution while it is stirred. The iodine color persists in the solution for several minutes at room temperature. A solution of 3.0 g. of tetramethylammonium chloride in 20 ml. of methanol is then added to the reaction mixture and the white precipitate which forms is separated by filtration. The solid is crystallized from water and bis(tetramethylammonium) tetraiodohexahydrodecaoorate(2) is obtained as a white crystalline compound which has the formula [(CH3)4N]2B1QHI4.

AnaIysis.-Calcd for C H B L N B, 14.05; 1,660. Found: B, 13.27;I, 66.47.

EXAMPLE 7 A reaction vessel is charged with ml. of C H OH and 10.0 g. of (NHfl B I-l Suflicient water is added to dissolve the (NI-IQ B I-I completely. The amount of water required is very small. The solution is cooled to 510 C. and crystalline iodine is added gradually in small portions with stirring until the color of iodine in the solution persists for 3-4 minutes. A total of 44.0 g. of iodine is added. The solution is stirred until it is colorless and it is then divided into two equal parts, identified as Fraction A and Fraction B.

Fraction A.Excess aqueous CsF solution is added to this fraction to form a gummy precipitate. The precipitate is separated by filtration and the solid is crystallized twice from water to yield 1.9 g. of a slightly gray powdery solid which is dicesium heptahydrotriiododecaborate(2), i.e., Cs B H I The identity of the compound is confirmed by elemental analysis.

Analysis.-Calcd for CS B H I Cs, 34.9; B, 14.18; I, 50.0. Found: Cs, 35.8; B, 14.0, 13.9; I, 49.28, 49.08.

The filtrate from the first separation is mixed with a large excess of aqueous CsF solution. A gummy precipitate forms which is redissolved in water and mixed with an aqueous solution of (Ch NCl. The precipitate so obtained is crystalline in character and it is separated by filtration to obtain crude bis (tetramethylammonium) heptahydrotriiododecaborate(2*), i.e., [(CH ).,N] B H I A portion (4.0 g.) of [(CH N] B H I is dissolved in boiling water and the solution is passed through an acidic ion-exchange resin column of the type described in Example A, Part C. The acid efiluent is titrated to a pH value of 7 with 0.1 N NaOH. The neutral solution is evaporated to dryness to obtain NflgBmHqIa as a white crystalline solid.

Fraction B.This fraction is heated to reflux and sulficient iodine is added to retain iodine color after one hour of refluxing. The alcohol is removed by evaporation under reduced pressure and the liquid residue is filtered to remove ammonium iodide. The filtrate is diluted with an equal volume of water and filtered again. An excess of aqueous 50% cesium fluoride solution is added to the filtrate and the viscous mass which forms is separated by filtration. The mass is triturated repeatedly with cold water and it is then crystallized twice from hot water. There is obtained 4.1 g. of a white powder which is dicesium tetrahydrohexaiododecaborate(2), i.e.

2 1o 4 s The identity of the compound is confirmed by elemental analysis.

AnaIysis.Calcd for Cs B H I Cs, 23.2; B, 9.50; I, 66.9. Found: Cs, 23.1; B, 9.28; I, 66.92.

1 7 EXAMPLE 8 A solution of iodine in methanol is added slowly with stirring to a solution of 0.62 g. of di(isopropylammonium) decahydrodecaborate (2-) (CH CNH B H in methanol until the color of iodine persists in the reaction mixture for several minutes at room temperature (ca. 25 C.). The addition of bromine to the reaction mixture is then begun and the mixture is heated to refluxing temperature. Addition of bromine is continued until the color of excess bromine persists in the refluxing mixture for a few minutes. A solution of 2.0 g. of tetramethylammonium chloride in methanol is added to the reaction mixture which is then chilled in an ice-water bath. The solid product which precipitates is separated by filtration and it is extracted with water to remove soluble products. The water-insoluble portion is a white crystalline compound which is his (tetramethylammonium) monobromopentaiodotetrahydrodecaborate(2*), a compound of the formula [CH N] B H BrI The identity of the compound is confirmed by elemental analysis.

Analysis.-Calcd for CgH2 B1 BII5N2: Br, I, Found: Br, 7.81; I, 63.16.

EXAMPLE 9 A reaction vessel is charged with about 150 ml. of methanol and 6 g. of (NH B H The mixture is refluxed and iodine is added gradually until reaction is complete as shown by the presence of a stable iodine color. Methanol is removed under reduced pressure, leaving a gummy reaction mass. Iodine monochloride (150 g.) is added directly to this mass and the mixture is heated to 80 C. for 3 hours. The mixture is cooled and it is extracted with CCL, and CS to remove 1G1 and iodine. The residue is dissolved in water, the solution is filtered and the filtrate is neutralized with NH OH. A concentrated aqueous solution of CsF is added until no further precipitation occurs. The precipitate is collected and it is crystallized from hot water. The product is a double salt of cs B l and C51. The identity of the product is confirmed by elemental analysis.

Analysis.Calcd for Cs B 'l -Csl: Cs, 20.93; I, 73.3; B, 5.67. Found: Cs, 18.8; I, 73.98; B, 6.35.

A portion of the double salt is dissolved in water and the aqueous solution is passed through a column packed with a commercial acidic ion-exchange resin. The aqueous efliuent is evaporated under reduced pressure to yield white crystals of dihydrogen decaiododecarborate (2") containing 8 moles of water of hydration of which two moles are considered to be associated with the protons.

Analysis.Calcd for (H30)2B10I10'6H20Z B, I, 83.5; N.E., 761. Found: B, 6.99; I, 83.51; N.E., 751, 754.

Examples 1 through 9 illustrate the compounds of the invention in which X is halogen and the process for preparing them. The process is generic to the preparation of halogen-containing compounds, e.g., Cs B H F 4)2 10 4 s 2 3)2 1 m 2 5)4 ]2 10 1o. 3)4 10 1o 2 1o 5 5 2 )4 1o 4 e 22 10 10 and the like. Compounds "having mixed halogen substituents are obtained by halogenating the decahydrodecaborate(2) salt partially with one halogen, e.g., chlorine, followed by halogenation with a second halogen, e.g., fluorine or iodine. Examples of compounds obtained by this mode of operation are and the like. The process can be extended to include all of the halogens.

EXAMPLE 10 (A) A reaction vessel is charged with g. of

and 100 ml. of HC(O)N(CH The mixture is stirred at about C. until the boron compound is dissolved and, with continued stirring, gaseous hydrogen chloride is bubbled through the solution. The temperature rises spontaneously to 126 C. over a period of 12 minutes and it then decreases to about C. Flow of hydrogen chloride is stopped at this point and the solution is filtered to remove the ammonium chloride which precipitates in the reaction. The clear filtrate is added with stirring to a solution consisting of 400 ml. of ethanol, 10 ml. of methanol, and 45 g. of cesium hydroxide. A white solid precipitates and it is separated by filtration. The solid is extracted with ml. of hot water. The portion remaining after extraction is crystallized three times from solution in hot water to obtain cesium dimethylformamidenonahydrodecaborate(l), which is used as a reactant in the second step of the process.

Analysis.Calcd for CsB H I-IC(O)N(CH Cs, 41.0; B, 33.4; C, 11.1; H, 5.0; N, 4.3. Found: Cs, 39.5; B, 32.7; C, 11.3; H, 5.1; N, 4.4.

The above compound is dissolved in a minimum quantity of water and slightly more than one equivalent of sodium hydroxide in aqueous solution is added with stirring. The solution is warmed on a steam bath for 2 hours. At the end of this time an excess of an aqueous solution of cesium hydroxide is added with stirring and the solution is poured into three times its volume of ethanol. Dicesium monohydroxynonahydrodecaborate(2), i.e., Cs B H OH, precipitates. It is separated by filtration and it is purified by recrystallization from water.

(B) A portion (4.0 g.) of the cesium salt,

obtained as described in Example 30 Part B, is dissolved in 60ml. of water and 1.0 g. of NaBH, is added to the solution. The mixture is allowed to stand overnight (about 18 hours) at atmospheric temperature and it is then heated on a steam bath until bubbling ceases. The solution is added to 200 ml. of ethanol containing 3 g. of CsOH. The precipitate which forms is separated and crystallized from water to obtain needle-like crystals of Cs B H OH. The infrared absorption spectrum confirms the presence of the OH group.

Ana[ysis.-Calcd for Cs B H OH: Cs, 66.5; B, 27.0; H, 2.5. Found: Cs, 63.9; B, 26.30, 26.43; H, 2.67, 2.92.

(C) A portion of the cesium salt,

prepared as described in Example 30, Part B, is dissolved in water and the solution is mixed with an aqueous solution of NaBH The mixture is allowed to stand overnight and it is then heated on a steam bath until bubbling ceases. An aqueous solution of TlNO is added with stirring and the precipitate which forms is separated. The product is crystallized from hot water to form gleaming white crystals 0f TIZBIQHQOH- (D) The compound CsB H -HC(O)N(CH prepared as described in Part A, is mixed with liquid ammonia. The mixture is stirred and it is evaporated to dryness. The residue is dissolved in water and the solution is mixed with an aqueous solution of TlNO The precipitate which forms is separated to obtain TIQBNHQOH as a white crystalline solid.

(E) The compound CsB H -HC(O)N(CH 2 is mixed with an aqueous solution of sodium hydroxide. The mixture is allowed to stand for a short period of time and it is then mixed with a solution of TlNO The precipitate is processed as described earlier to obtain T1 B H OH.

(F) A portion (4.0 g.) of Cs B I-I OC(O)H, obtained as descriped in Example 30, Part B, is dissolved in 60 ml. of water containing 5 g. of sodium hydroxide. The solution is refluxed for 2 hours, cooled, chilled and filtered to separate the solid. There is obtained 36 g. of Cs B H OH. A portion (20 g.) of this compound is dissolved in hot water and passed through an acidic ion-exchange resin of the type described earilier to obtain the acid in aqueous solution. The acidic solution is neutralized with aqueous sodium hydroxide solution and the neutral solution is evaporated to dryness. There is obtained 9.0 g. of Na B H OI-I as a white, hygroscopic crystalline salt.

(G) An aqueous solution of H B H OH, prepared by a process of the type described in Part F is neutralized to a pH value of 7 with an aqueous solution of (CH NOH The solution is evaporated to dryness under reduced pressure to obtain pure bis(tetramethylammonium) monohyd roxynonahydrodecaborate 2) Analysis.- Calcd for [(CH N] B H OH: C, 34.0; H, 12.0; B, 38.2; N, 9.9. Found: C, 33.97, 34.02; H, 12.28, 11.82; B, 38.20, 38.05; N, 9.35.

EXAMPLE 11 (A) A reaction vessel, equipped with a stirrer and a condenser, is charged with 20 g. of (NHQ B H 22 ml. of concentrated hydrochloric acid and 150 ml. of N- methyl-2-pyrrolidone. The mixture is stirred and it is heated until 20 ml. of water is removed by distillation. The final pot temperature is 170 C. The reaction mixture is cooled to about 25 C. and it is filtered to remove any solid material which may be present. The filtrate is poured with stirring into 800 ml. of water. A solid forms which is separated by filtration to yield 3.0 g. of bis(N-methyl- 2-pyrrolidone) decaborane(8), a compound of the following structure:

ll CCII2 BmHsZCHsN Analysis.-Calcd for B H -2N(CH )(CH CO: C, 38.2; H, 8.3; N, 8.9. Found: C, 38.8, 39.0; H, 8.6, 8.8; N, 8.8, 8.3.

(B) A portion 1.0 g.) of bis(N-methyl-Z-pyrrolidone) decaborane(8), obtained as described in Part A is suspended in an aqueous solution of NaOH. The suspension is boiled until the compound dissolves. The solution is filtered while hot and the filtrate is cooled. An aqueous solution of TlNO is added to the filtrate and the yellow precipitate which forms is separated by filtration. The product is washed and dried to obtain dithallium dihydroxyoctahydrodecaborate (2). The identity of the compound, which has the formula Tl B I-I (OH) is confirmed by its infrared absorption spectrum.

(C) The process of Part B is repeated to the point where the solution is filtered and cooled. Aqueous CsOI-I is added to the filtrate and the white precipitate which forms is separated. The solid is crystallized from water to obtain dicesium dihydroxyoctahydrodecaborate(2), i.e., Cs B H (OH) The identity of the compound is confirmed by its infrared absorption spectrum. The infrared spectrum shows characterizing OH absorption bands at 2.8 and 3.0 z; other absorption bands are noted at 4.0, 4.1, 6.0 and 6.3,u.

(D) A suspension is prepared containing 10.4 g. of bis(N-methyl 2 pyrrolidone) decaborane(8), 3.5 g. of NaOH and 100 ml. of water. The suspension is refluxed for 10 minutes at which time all of the solid is dissolved. The solution is warmed under reduced pressure until the volume is about ml. A solution consisting of 22 g. of CsOH in ml. of water is added at this point with stirring and the resulting mixture is poured into 210 ml. of methanol. The solid which forms is separated and it is mixed with stirring with fresh methanol for a short time on a steam bath. The solid is separated again and it is recrystallized from water to obtain pure C52B10H8 OH 2 as a triliydrate.

Artalysis.Calcd for Cs B H (OH) -3H O: Cs, 56.6; B, 23.0; H, 3.4. Found: Cs, 56.4, 55.6; B, 24.30, 24.45; H, 3.24.

(E) A reaction vessel is charged with 20 g. of bis(N- methyl-2-pyrrolidone)decaborane(8), 7 g. of NaOH and 150 ml. of water. The mixture is refluxed for 2 hours and the solution is poured into an ethanol solution of (CH NOH. The clear solution is distilled to remove the ethanol and the liquid which remains (about ml.) is poured into 500 ml. of propanol. An oil separates and is removed. The oil solidifies when stirred with a small quantity of ethanol. The solid is crystallized from aqueous ethanol, the crystals are dissolved in methanol and the solid is reprecipitated with ethanol. The mixture is warmed on a steam bath to complete crystal formation, the crystals are separated by filtration and dried under re duced pressure to obtain bis(tetramethylammonium) dihydroxyoctahydrodecaborate(2).

Analysis. Calcd for [(CH N] B H (OH) C, 32.2; H, 11.4; B, 36.2; N, 9.4. Found: C, 30.42, 30.16; H, 11.36, 11.40; B, 35.92, 36.00; N, 8.71, 8.79.

An aqueous solution of the crude tetramethylammonium salt obtained in the reaction is mixed with an aqueous solution of TlNO to precipitate the thallium salt. The product is separated and crystallized from water.

Analysis. Calcd for Tl B H (Ol-l) Tl, 72.9. Found: Tl, 70.4.

(F) The process of Part E is repeated, employing 27 g. of bis(N-methyl-Z-pyrrolidone)decaborane(8), 7.5 g. of NaOH and 100 ml. of Water. The mixture is refluxed for 5 hours and one-half of the solution is poured into 400 ml. of propanol containing 21 g. of (CH NOH'5H O. The oil which separates is processed, as described earlier, with ethanol to obtain the tetramethylammonium salt.

Analysis. Calcd for [(CH3)4N]2B1QH;;(OH)2I C, 32.2; H, 11.4; B, 36.2; N, 9.4. Found: C, 31.96, 32.28; H, 11.59, 11.42; B, 35.98, 36.07; N, 8.58.

Examples 10 and 11 illustrate the compounds of the invention in which X is hydroxyl, i.e., OH, and their preparation. The process is generic to the preparation of hydroxyl-substituted decaborates, e.g.,

A solution of nitrous acid is prepared by dissolving 4.14 g. of sodium nitrite in 60 ml. of 1 N hydrochloric acid. The solution is cooled to approximately 0 C. in icewater and there is added to it slowly and with vigorous stirring a solution of 1.5 g. of bis(tetramethylammonium) decahydrodecaborate(2) in 25 ml. of water. A dark brown solution is obtained which contains brown solid material. The solid material is isolated by filtration. Care must be exercised in the isolation step as the solid is explosive and, when dry, detonates on touching with a rod. The filtrate, free of solid, is treated with an excess of an aqueous solution of tetraethylammonium bromide. A brown solid precipitates which is separated by filtration. This product is sensitive to shock and it must be handled with caution. The infrared absorption spectrum of the compound shows bands for substituents having nitrogenoxygen bonds, for the diazoniurn group (+NEN) (4.5 1) and for B-H bonds (4.2 The compounds contain 13.42% nitrogen.

EXAMPLE 13 (A) Nitric acid (concentrated) is added carefully and slowly With vigorous stirring to an aqueous solution (50%) of the free acid, (H O) B H -H O, until the reaction mixture becomes dark blue. The addition of nitric acid is stopped and a vigorous (almost violent) reaction develops. When the reaction subsides a dark red solution remains. The compound present in the solution is the hydrate of. dihydrogen pentanitropentahydrodecaboratc -l (HBO)ZBIOH5(NOZ)5' At this point the solution can be used directly to dye acid-modified poly(acrylonitrile) fibers an attractive shade of red. Addition ofaqueous sodium carbonate to the solution to bring it to a pH value of 4-5 provides a dye bath which is useful for dyeing polyamide fibers obtained from hexamethylenediamine and adipic acid, and viscose fibers. The shade obtained on the fibers is determined by the pH of the dyeing solution. For example, in a slightly acidic solution viscose rayon is dyed orange or red; in a basic solution, viscose rayon is dyed blue.

The aqueous solution of the compound, obtained as described above, is useful as an acid-base indicator. The solution is red when acidic, blue-green when weakly alkaline and dark blue when strongly alkaline.

Upon adding an aqueous solution of tetramethylammonium chloride to the dark red reaction mixture, obtained as described in the first paragraph, a dark precipitate is obtained which is very shock-sensitive and which detonates readily when dry. The compound is bis(tetramethylammonium) pentanitropentahydrodecaborate(2), i.e.,

The procedure, as described above, is applicable to the preparation of other pentanitrodecaborate salts. Thus, diammonium decahydrodecaborate(2-), (NHQ B H reacts vigorously with nitric acid to give principally (NI-I B H (NO Other pentanitrodecaborate salts which are obtained from appropriate reactants are (B) A solution of 0.25 g. of cupric nitrate in ml. .of water is added to a solution of 0.5 g. of diammonium decahydrodecaboratefl") in 15 ml. of Water which has been acidified with dilute nitric acid. After two minutes an additional 1.0 g. of cupric nitrate is added to the solution and, after another two minutes, half of the reaction solution is added to 10 ml. of a saturated solution of cupric nitrate. A very intense blue color develops in the solution in a few minutes. The solution contains the copper salt of a nitrated decaborate(2). The tetramethylammonium salt precipitates upon addition of aqueous tetramethylammonium chloride solution to the blue reaction mass; addition of cesium chloride results in precipitation of the cesium salt.

Examples 12 and 13 illustrate compounds of the invention in which X is a nitrogen-oxygen group and their preparation. The process is generic to the preparation of compounds bearing these substituents. To illustrate, it can be used to prepare Li B H NO,

BHBIOH7(NOZ)3, PbB H6(NO2)4, and the llkC.

EXAMPLE 14 (A) A mixture of an aqueous solution of (about 0.1 mole) and 100 ml. of dimethylformamide is reacted and processed as described in Example 30, Part A.

The less soluble fraction is recrystallized from water to obtain needle-like crystals of tetramethylammonium hydrogen dimethylaminononahydrodecaborate (2').

Analysis.-Calcd for [(CH N]HB H (CH B, 45.7; C, 30.5; H, 11.9; N, 11.8. Found: B, 44.1; C, 31.6; H, 11.6; N, 11.8.

The above tetramethylammonium salt is dissolved in hot water and an aqueous solution of TlNO is added with stirring. The solid which forms is separated and recrystallized from water'to obtain thallium hydrogen dimethylaminononahydrodecarborate (2) Analysis.Calc-d for TlI'IB H N(CI-I t Tl, 55.7. Found: Tl, 54.5.

(B) The process is repeated as described in Example 30, Part B, and the less soluble fraction is dissolved in water and an aqueous solution of trimethylsulfonium iodide is added with stirring. The solid which precipitates is separated by filtration and it is crystallized from water to obtain trimethylsulfonium hydrogen dimethylaminononahydro decaborate 2*).

Analysis.-Calcd for (CH SHB ,H N(CH C, 25.1; B, 45.2; H, 10.5; S, 13.4; N, 5.85. Found: C, 24.34, 25.78; B, 45.07; H, 10.33, 10.44; S, 13.78; N, 5.95.

Example 14, in combination with Example 30, illustrates the compounds of the invention in which X is an amino group. The process is generic to the preparation of amino-substituted decaborates and compounds having a range of amino groups can be obtained by the choice of an appropriate amide. To illustrate, the hydrate of dihydrogen decahydrodecaborate can be reacted (1) with formamide and then with CsF to yield CsHB H NH (2) with diethylformamide and TlNO to yield 10 9 2 5)2 (3) with monopropylformamide and (CH NOH to yield (CH NHB H NHC I-I (4) with dicyclohexylformamide and (CH SI to yield 3) a 10 9 6 11)2 and (5) with diallylformamide and LiOH to yield is passed through an acidic ionexchange column as described in Part D of the same example to obtain an aque- I ous solution of the acid H B H Cl This acid can be reacted as described in Examples 14 and 30 (1) with HC(O)N(CH and (CH NOH to obtain and (2) with HC(O)NH and (CH PI to obtain (CH3)4PHB1QHC13NH2.

EXAMPLE 15 A reaction vessel is charged with 7 ml. of 2-propanol and it is cooled in an ice-bath while 9 g. of a viscous aqueous solution of H -B H is added gradually. The temperature remains at 25 C. or lower during the addition. The solution is cooled to 10 C. and 5 g. of styrene monomer is added slowly with stirring. A slight temperature rise is noted (not over 15 C.) and the solution is stirred for 2 hours with ice-bath cooling, then for 2 more hours at prevailing air temperature (25 C.). The solution is neutralized with aqueous 10% NaOH solution and it is steamdistilled for 20 minutes. The solution is concentrated in a rotary evaporation unit to a slush. An aqueous 50% solution of CsF is added with stirring and the precipitate which forms is separated. It is crystallized from hot water to obtain a product consisting of about 2 1o s( -2 4 s 5)2 and 20% 2 1o 9( 2 4 s 5) The presence of cesium is confirmed by flame photometry. AnaIysis.Calcd for 80:20 composition: C, 30.3; H, 4.3; B, 18.9. Found: C, 30.55; H, 5.27; B, 18.01.

EXAMPLE 16 A Carius tube (capacity, 50 ml.) is charged with 7 g. of the dihydronium salt of decahydrodecaborate(2) [(H O) B H 0.9 ml. of water, 3 ml. of isopropyl alcohol and 8 g. of propylene. The charged tube is placed in a tumbler mixer and it is tum-bled at about 25 C. for 8 hours. The tube is allowed to stand three days at prevailing atmospheric temperature (ca. 2025 C.). It is then heated at 8090 C. for 16 hours. The tube is cooled to about '78 (3., opened, and it is allowed to warm to atmospheric temperature. Unreacted propylene evaporates during this period. The contents remaining in the tube are extracted with 1-0 ml. of ether and the ether extract is allowed to evaporate. A yellow-brown residue remains which is dissolved in 20 ml. of ether and the ether solution is washed with 20 ml. of water. The ether layer is dried and the ether is permitted to evaporate. There remains a thick yellow syrup which is dihydrogen bis(isopropyl)octahydrodecaborate(2) trihydrate, i.e.,

The identity of the compound is confirmed by its infrared spectrum and by elemental analysis. The infrared spectrum shows a strong BH absorption at 3.9; medium C-H absorption at 3.4, 6.9 and 7.2a and 'broad skeletal absorption at 9.1;.

Analysis.Calcd for C H B O C, 27.88; H, 11.70; B, 41.86. Found: C, 29.57; H, 10.34; B, 40.10.

The process of Example 16 can be used to prepare other alkyl-substituted decaborates. To illustrate, by employing the appropriate olefin, there can be obtained It is noted in the process of Example 16 that no catalyst is employed. The hydrated acid decahydrodecaborate has suflicient acidity to serve as its own catalyst in the alkylation process.

EXAMPLE 17 A portion (0.3 g.) of the product of Example 16 is heated one hour on a steam bath with 4 ml. of a 5% sodium hydroxide solution. A clear lut n s b i to which 4-5 drops of a 50% aqueous solution of cesium fluoride is added. A yellow microcrystalline solid is formed which is separated by filtration. The product is dicesium bis(isopropyl)octahydrodecaborate(2)monohydrate, Cs B H [CH(CH -H O. The identity of the compound is confirmed by the infrared absorption spectrum and by elemental analysis. The infrared absorption spectrum shows weak bands at 8.55, 9.0 and 11.9 which is characteristic of the isopropyl group.

EXAMPLE 18 (A) A reaction vessel is charged with about 8.0 g. of hydrated H B H and 8 g. of methanol at 0 C. Phenylacetylene (4.0 g.) is added and the mixture is shaken. It is maintained at 0 C. for 3 hours with intermittent shaking to assure intimate mixing and it is then allowed to stand at atmospheric temperature (about 25 C.) for hours. Aqueous CsOI-I solution is added with stirring to the reaction mass until it is neutral. The mixture is cooled in ice-water and it is filtered to separate the precipitate. The product is extracted three times with boiling water, using volumes of 75 ml., 40 ml. and ml., respectively. Each extract is cooled in ice and the precipitate which forms is separated. Each portion is recrystallized from boiling water and they are shown to be the same product by their infrared absorption spectra. The products are the dicesium salts of nonahydrodecaborates which have a hydrocarbon substituent of 8 carbons obtained from phenylacetyleue.

Elemental analysis of the product is as follows: C, 18.76; H, 3.89; B, 21.73.

(B) The product obtained in the second extraction of the product of Part A is dissolved in boiling water and aqueous TlNO solution is added with stirring. The precipitate which forms is separated and it is extracted with boiling water in a soxhlet unit for 50 minutes. The product is dried and it is shown by the infrared absorption spectrum and elemental analyses to be the dithallium salt of the decaborate anion described in Part A.

Elemental analysis of the product yields the following data: C, 15.2; H, 3.1;B, 18.0.

EXAMPLE 19 A reaction vessel, equipped with reflux condenser, is charged with 10 g. of the hydrate of H B H i.e., (H O) B H 50 g. of octadecene-l and 50 ml. of 1,2- dimethoxyethane. The mixture is stirred and heated to refluxing for 24 hours. On cooling, the vessel is filled with light, yellow-brown waxy crystals. The solvent is evaporated from the reaction mass under reduced pressure and the crystalline residue is washed with 500 ml. of pentane. The product is dried thoroughly under reduced pressure to obtain 8.5 g. of the hydrate of dihydrogen bis(octadecyl)octahydrodecaborate(2 a yellow crystalline solid which decomposes at 260270 C. without melting.

Analysis.Ca1cd for (H3O)2B1UH8(C13H37)21 C, H, 12.5; B, 3.45. Found: C, 73.24; H, 13.35; B, 3.83.

EXAMPLE 20 A solution containing 9 g. of (NH B H in 50 ml. of water is passed through a column packed with an acidic ion-exchange resin of the type described previously. The acidic eluate is evaporated under reduced pressure and the residue is dried at 0.1 mm. pressure to yield the dihydrate of H B H i.e., (H O) B H as a slightly gray solid.

A reaction vessel, equipped with a reflux condenser, is charged with the acid obtained above, 70 ml. of 1,2-dimethoxyethane and 5 ml. of water. The mixture is stirred to form a solution and 15 ml. of 2,3-dimethyl-1,3-butadiene is added. The reaction mixture, which consists of two layers, is refluxed for 6 hours. The mixture becomes light green in color but it remains as two layers. It is transferred to a pressure vessel (225 ml. capacity) and heated for 16 hours at C. under autogenous pressure. The tube is cooled in liquid nitrogen and vented to release gaseous products through a vacuum system. Non-condensable products are released which are principally hydrogen. The liquid residue in the pressure vessel is evaporated to yield a yellow syrup. The syrup is dissolved in 15 ml. of hot 5% aqueous KOH solution and 8 ml. of a 50% CsF solution is added. A sticky light yellow precipitate forms which is separated and recrystallized to obtain an almost white crystalline solid which is Analysis.-Calcd for above compound: C, 8.13; H, 3.87; B, 24.41. Found: C, 7.86, 7.66; H, 3.89, 3.80; B, 23.7 8.

The compound is tetracesium 2,3-dimethylbntane-l,4-

bis(nonahydrodecaborate). The substituent X in this compound is viewed as CH CH (CH CH CH CH B H Cs EXAMPLE 20A (A) Nine grams of the acid, (H O) B H -H O, is added carefully to a solution of 40 ml. of cyclohexene in 60 ml. of 1,2-dimethoxyethane. After the initial vigorous exothermic reaction has subsided, the mixture is refluxed for 2 hours. The mixture is red and separates into two phases. Water ml.) and pentane (50 ml.) are added and a third phase forms. This phase is separated and the solvent is removed under reduced pressure to yield a viscous cherry-red liquid which is the hydrate of dihydrogen bis(cyclohexyl)octahydrodecaborate (2), i.e.,

2 10 8( 6 11)2' 2 The identity of the compound is confirmed by its infrared absorption spectrum. The compound is soluble in ethanol, ether and tetrahydrofuran; insoluble in water and pentane.

(B) The compound of Part A is dissolved in hot 10% NaOH solution and aqueous 50% cesium fluoride solution is added with stirring. A gummy, off-white precipitate forms which is separated and recrystallized from wa- 25 ter to give dicesium bis(cyclohexyl)octahydrodecaborate (2'), i.e., Cs B H (C H 'H O, an Off-White crystalline solid.

Compounds of the type described in Examples 17 and 20-A, Part B, show surface-active properties in aqueous solutions and they are useful as surface-active agents. To illustrate, water containing a minor amount of the compound of Example 20-A, Part B, forms a long-lasting blanket of foam when agitated.

Examples 15-20-A illustrate the compounds of the invention in which X is a hydrocarbon group. The group can be saturated or unsaturated, it can be open-chain or cyclic. The process is generic to the preparation of compounds bearing hydrocarbon substituents by reaction of an aqueous or alcoholic solution of H B H with an appropriate olefinic or acetylenic hydrocarbon. To illustrate, an aqueous solution of H B H can be reacted (1) with methylstyrene and NaOH to yield (2) with ethylene and (C H CH (CH SOH to yield [(CGHSCHQ) (CH3)2S]2B10HQC2H5, cyclohexene and CsF to yield cS2B10H9C H11, and (4) with octadecene-l t (H3O)2B10H9C1BH37.

EXAMPLE 21 A reaction vessel is charged with 12 g. of hydrated HZBIOHIO The reaction mass is stirred and 10 g. of propiolic acid is over a period of two hours. The temperature of the reaction mixture rises slowly to 30-35 C. in this time and, after the addition of the propiolic acid is complete, the mixture is warmed to 40 C. for 30 minutes. Aqueous 5% NaOH solution is'added to the viscous mass until it is slightly alkaline. The solution is evaporated to a volume of 40 ml., an aqueous solution of cesium fluoride is added with stirring, and the precipitate which forms is separated by filtration. The solid so obtained is dried under reduced pressure and it is crystallized from water two or three times. The product is a mixture of cesium salts of nonahydrodecaborates which have a carboxylbearing hydrocarbon group of 2 carbons obtained from propiolic acid. On the basis of infrared absorption spectra, the carboxyl-substituted hydrocarbon group is saturated in some instances and, in others, it is unsaturated, i.e., olefinic.

The elemental analysis is as follows: Cs, 62.0; H, 3.12; C, 5.17.

An aqueous solution of the above product can be passed through a column packed with an acidic ion-exchange resin to yield an aqueous solution of the acid of the abovedescribed anion. In view of the presence of the carboxylbearing substituent on the decaborate anion, the acid will be tribasic.

Example 21 illustrates the compounds of the invention in which X is a substituent which has a functional group that can undergo further reactions. Thus, the -COOH group in the compound of Example 21 can be reacted by well-known methods to form an ester, an amide, a nitrile or a salt (ammonium, substituted ammonium, hydrazinium, substituted hydrazinium, and the like). The process of Example 21 is generic to the preparation of compounds in which X bears a functional group. To illustrate, H B H is reacted (1) with acrylonitrile and to obtain (NH4)2B10H9CH2CH2CN, with methyl acrylate and NaOH to yield and (3) with N,N-dimethyl acrylamide and CsF to yield Cs B H C H C(O)N(CH Each of the above compounds in aqueous or alcohol solution can be reacted with an acidic ion-exchange resin to yield aqueous or alcohol solutions of the acids, i.e., H B H CH CH CN,

26 and H B H C H C(O)N(CH Solutions of these acids can, of course, be neutralized with any base to form the corresponding salt.

EXAMPLE 22 (A) A solution of 25 g. of (NHQ B H in 180 ml. of water is passed through a column packed with about 1080 g. of acid ion-exchange resin (Amberlite IR- H). The column is rinsed with water to provide 305 ml. of eflluent. The effluent is evaporated to about 50 ml. under reduced pressure at a temperature of less than 44 C. A viscous liquid remains which is cooled in an ice bath to 10 C. and 100 ml. of 1,2-dimethoxyethane (glyme) is added with stirring. The solution changes to light green in color and its temperature rises to about 38 C. Stirring and cooling is continued until the temperature drops to 25 C. at which time 12 ml. of benzoyl chloride is added. The temperature remains unchanged and the color of the solution becomes orange red. The solution is stirred about 4 hours in an ice bath and then for 1.5 hours at prevailing atmospheric temperature. The total volume is ml. of a clear, dark red liquid.

(B) A portion (30 ml.) of the reaction liquid is mixed with 54 ml. of an aqueous solution of CsOH (prepared by dissolving 45 g. of CsOH in 100 ml. of water). A light yellow solid which precipitates is separated by filtration and the filtrate is mixed with an aqueous solution of (CH NOH. The yellow precipitate is separated and it is crystallized from hot water to obtain 1.6 g. of cesium tetramethylammonium monobenzoylnonahydrodecaborate(2 i.e., CS(CH3)4NB10H9C(O)CH5. The of the compound which is a macrocrystalline solid, is confirmed by elemental analysis.

Analysis.-Calcd for (CH NCsB H C(O)C H Cs, 31.0; C, 30.8; H, 6.1; B, 25.2; N, 3.3. Found: Cs, 3-1.5; C, 27.8, 28.2; H, 5.6, 5.8; B, 24.8; N, 3.2, 3.0.

(C) A second portion (50 ml.) of the reaction mixture is poured with stirring into a solution of 12 g. of (CH NCl in 70 ml. of CH O'H. The precipitate which forms is separated and it is washed with CH OH to obtain 3.0 g. of [(CH N] B H A portion of the filtrate is mixed with aqueous (CH NOH until the color changes from dark red to very light orange. The mixture is poured into ethanol and the cream-colored precipitate which forms is separated. The solid is crystallized from aqueous ethanol to obtain 2.3 g. of

The identity of the compound is confirmed by elemental analysis.

Analysis.Calcd for [(CH3)4N]2B10H9C(O)C6H5: C, 48.6; B, 29.2; H, 10.3; N, 7.58. Found: C, 45.1, 46.3; B, 29.8, 29.8; H, 10.4, 10.4; N, 7.2, 7.4.

A second portion of the filtrate is poured into 50 ml. of ethanol and the mixture is cooled in an ice bath. The orange colored solid which forms is separated to obtain 0.15 g. of the hydrate of hydrogen tetramethylammonium monobenzoylnonahydrodecaborate(2-); the compound forms acidic solutions. Its identity is confirmed by elemental analysis.

Analysis.Calcd for C, 41.8; B, 34.3; H, 9.2. Found: C, 41.0, 41.4; B, 34.0, 34.0; H, 10.8, 10.5.

(D) A small quantity of is mixed with a few milliliters of methanol and water is added dropwise and with stirring until substantially all of the solid has dissolved. The solution is filtered and an aqueous solution of cesium hydroxide is added. The solid which precipitates is separated by filtration, recrystallized from hot water on a steam bath and washed thoroughly with ice-water. It is dried in vacuo to obtain cesium tetramethylammonium monobenzoylnonahydrodecarborate(2) as a crystalline compound.

AnaIysis.-Calcd for Cs(CH NB l-I C(O) C H C, 30.79; H, 6.11; B, 25.2. Found: C, 30.37, 30.32; H, 6.13, 6.41; B, 24.73, 24.79.

(E) An aqueous solution of is passed through a column packed with an acidic ionexchange resin of the type described earlier and the aqueous efiluent is titrated carefully with aqueous NaOH. The progress of the titration is followed with a pH meter to determine the characteristics of the acid which is present in the acid eflinent. The curve shows only one break up to a pH of 11, the break occurring at the neutral point. The behavior of H B H C(O)C H is that of a strong acid in which both protons (H are equivalent.

The above procedure is repeated employing 5.0 g. of [(CH N] B H C(O)C H and titrating the acidic efliuent to a pH of 7 with aqueous cesium hydroxide. The solution is evaporated under reduced pressure until a solid begins to precipitate. The solution is filtered and the filtrate is chilled in an ice-ethanol bath. A white solid forms which is separated to yield a monohydrate of dicesium monobenzoylnonahydrodecab orate 2").

Analysis.-Calcd for CSZBIQI'IQC(O)C$H5'HZO1 CS, 53.3. Found: Cs, 52.9.

(F) A portion of the compound,

obtained as described in Part A above, is dissolved in water and an aqueous solution of tetrapropylammonium hydroxide is added with stirring. The precipitate which forms is separated and it is crystallized from hot water to obtain bis(tetrapropylammonium) monobenzoylnonahydrodecaborate(2*) as a yellow crystalline product.

Analysis-Calcd for [(C3H7)4N]ZB1OHQC(O)CGH5: C, 62.56; H, 11.86; B, 18.18; N, 4.70. Found: C, 62.64, 62.76; H, 12.00, 11.96; B, 18.73, 18.62; N, 4.66, 4.73.

(G) A mixture of 2.0 g. of diammonium decahydrodecaborate(2) and 30 ml. of polyphosphoric acid is heated at 45 C. for a short time. Benzoyl chloride (1.8 ml.) is added to the solution with stirring to form a solution of orange-red color. The solution is heated with stirring to 60-65 C. for minutes and it is then poured into 100 ml. of water with vigorous stirring. An orange solid forms which is acidic and which is separated by filtration. The crude product is dissolved in hot chlorobenzene and it is reprecipitated by adding decahydronaphthalene or petroleum ether. The purified orange solid is dihydrogen di(benzoyl)octahydrodecaborate(2-), i.e.,

0 112B mind? c n.) 2

The identity of the compound is confirmed by elemental analysis.

Analysis.-Calcd for C H B O C, 51.1; H, 6.12; B, 32.9. Found: C, 49.82; H, 6.50; B, 27.42.

The compound is soluble in ace-tone, alcohol, dichlorobenzene, dioxane, and similar solvents. It is insoluble in water, petroleum ether, and other saturated hydrocarbons. Treatment of the compound with aqueous sodium hydroxide yields the sodium salt,

0 NlzBruHs (105115 2 Reaction of the sodium salt in aqueous solution with tetramethylammonium chloride gives itouumpn ir. com, 1 i.e., bis(letramethylammonium) dibenzoyloctahydrodecaborate(2). The identity of this compound is confirmed by elemental analysis.

Analysis.-Calcd for C H B N O B, 22.75. Found: B, 21.03.

By employing the process of Example 22,

(NH4)2B1OH10 and acetyl chloride are reacted to yield 0 I (NII-Q2B10I'I3 (J) C113 2 which is an orange-colored solid.

The process of Example 22 is broadly applicable to the preparation of acylated decaborates. For example, H B H with C H C(O)Cl yields Other compounds which can be obtained from the appropriate acid chloride are as follows:

EXAMPLE 23 (A) A solution of the acid (H O) B H is prepared as described in Example B, Part C. The elfiuent from the ion-exchange column, which has a volume of about 345 ml., is evaporated to a volume of about 50 ml. The solution is cooled to 05 C., ml. of 1,2-di1nethoxyethane is added with stirring, followed by 21 g. of benzoyl chloride. The mixture, cooled in an ice bath, is stirred for one hour at which time the ice bath is removed and stirring is continued at atmospheric temperature for about 48 hours. The color of the solution is dark red. The mixture is then poured into a solution of 40 g. of (CH NCl in 200 ml. of CH OH. An aqueous solution of (CH NOH is added to the filtrate until the color changes to pale yellow and a further slight excess of the base is added. The mixture is poured into 700 ml. of C H OH and the precipitate is separated by filtration. The product, weighing 23.5 g., is a cream-colored solid which is [(CH N] B H C(O)C H A portion (10 g.) of the above compound is dissolved in water and the solution is passed through a sodium ionexchange resin (Amberlite IR -Na form) to obtain a solution of Na B H C(O)C H The eilluent is evaporated to obtain 5.6 g. of the solid sodium salt, which is a hygroscopic, brittle, glass-like compound.

The sodium salt, in aqueous solution, is mixed with an aqueous solution of the hydrochloride of semicarbazide to form the scmicarbazone. The solution of the semicarbazone is mixed with aqueous (CH ),,NOH and the precipitate which forms is separated. The solid is crystallized from water to obtain the semicarbazone of [(CH N] B H C(O)C H The identity of the compound is confirmed by elemental analysis.

Alzalysis.Calcd for [CH N] B; H C(C H NNHC(O)NH -H O: C, 43.0; H, 9.71; B, 24.2; N, 15.7. Found: C, 43.64; H, 9.65, 9.83; B, 23.53; N, 15.29.

(B) A solution of 10g. of [(CH N] B H C(O)C H in water is passed through an acidic ion-exchange resin column to obtain as the efiiuent a solution of (H O) B H C(O)C H The effiuent is titrated to the neutral point with 0.1N NaOH and the resulting solution is evaporated to a volume of about 100 ml. under reduced pressure. At this point 10 g. of the hydrochloride of semicarbazide and 15 g. of sodium acetate are added and the solution is heated on a steam bath for about minutes. The solution is clear yellow and contains the Sodium Salt, N21 B H C(C H Aqueous solutions of (CH NOH and (CH NCl are added in large excess until a precipitate forms. The precipitate is separated by filtration and crystallized from water to obtain 7.7 g. of

The analysis of the compound (see Part A for calculated values) is as follows: B, 22.67, 22.71; C, 41.38, 41.58; N, 14.81, 14.93.

EXAMPLE 24 A reaction vessel is charged with ml. of an aqueous solution containing 4 g. of [(CH N] B H C(O)C H To this solution there is added with stirring 10 ml. of an aqueous solution containing 0.01 mole of phenylhydrazinc, and 5 ml. of glacial acetic acid. The yellow solid which precipitates is separated by filtration and dried. The compound so obtained is the trihydrate of the phenylhydra- ZQne of Analysis.-Calcd for C, 46.22; H, 8.90; B, 24.50; N, 9.51. Found: C, 48.15; H, 9.01; B, 24.52; N, 10.31.

Examples 23 and 24 illustrate compounds of the invention in which X is a substituent having a carbon-tonitrogen multiple bond, i.e., a C=N- group. These are derived readily from compounds having carbacyl substituents and the processes of Examples 23 and 24 are generic to the preparation of this type of compound.

EXAMPLE 25 A mixture of 1.3 g. of p-toluenesulfonyl chloride and 45 ml. of polyphosphoric acid is stirred at 80-90" C. for 2 hours. To this mixture there is added 1.0 g. of diammonium decahydrodecaborate(2-), (NI-IQ B H and the mixture is stirred and heated at 8090 for about hours. The mixture is then added with stirring to 100 ml. of water and a yellow solid precipitates. The solid, which is dihydrogen (p-tolylsulfonyl)nonahydrodecaborate(2), is separated by filtration and it is washed and dried in air. The identity of the yellow compound, which has the formula H B H SO C H CH is confirmed by elemental analysis.

AnaIysis.Calc"d for C H B sG z C, 30.6; H, 6.6; B, 39.4; S, 11.65. Found: C, 31.80; H, 7.05; B, 34.6; S, 11.05.

The procedure of Example is generally operable for the preparation of decaborates having arylsulfonyl groups as substituents. By employing the appropriate arylsulfonyl chloride, there can be obtained, e.g., I'I2B1gI'I3SO2C6H5, 3)4 2B10H9SO2C6H3(CH3)2:

is passed through an acidic ion-exchange resin of the type described earlier and the acid efiiuent is evaporated under reduced pressure to a volume of abcut 45 ml. To this solution, which contains (H O) B H-, 100 ml. of 1,2-dimethoxyethane is added with stirring. A blue color develops and the temperature of the mixture rises to 50 C. The solution is warmed on a steam bath at about 7080 C. for 45 minutes. The solution, which is yellow, is poured into a solution (300 ml. propanol and 100 ml. ethanol) containing excess (CH NOH. The white precipitate which forms is separated by filtration and it is dried overnight. There is obtained 31 g. of bis(tetramethylammonium) mono(2 methoxyethoxy)nonahydrodecaborate (2 L6,, The Compound is a crystalline White water-soluble product.

A portion of the above compound is dissolved in water and an aqueous solution of TlNO is mixed with it. The White precipitate which forms is separated and it is recrystallized from boiling water and from methanol to obtain Tl B H OCH CH OCH as gleaming white crystals. The identity of the compound is confirmed by elemental analysis.

Artalysis.Calcd for Tl B H OCH CH OCI-I C, 5.98; H, 2.66; Tl, 68.0; B, 17.99. Found: C, 5.23; H, 2.82; Tl, 65.93; B, 17.99.

The infrared absorption spectrum of the thallium compound suggests that the thallium ion forms a complex with the ,B-methoxyethoxy substituent.

(B) A reaction vessel is charged with 35 ml. of 1,2-dimethoxyethane containing in solution 0.03 mole of a hydrate of H B H Cyclohexanone (4 ml.) is added to the solution and the mixture is stirred at atmospheric temperature (about 25 C.). The initial light yellow color of the solution fades in about 20 minutes and 10 ml. more of cyclohexanone is added. The solution again becomes yellow and after 6 hours stirring it has a reddish tinge. The solution is allowed to stand for about three days and it is then medium dark red in color. The solution is added with stirring to a solution of 20 g. of (CH MNOH in 300 ml. of isopropyl alcohol. A solid precipitates which is separated by filtration to obtain a pink-colored powder, a red gum and a dark red filtrate. The gum is boiled in ethanol and the insoluble portion (1.7 g.) is separated by filtration. The solid is crystallized from methanol to obtain light pink crystals of bis(tetramethylammonium) (Z-rnethoxyetho-xy)nonahydrodecaborate(2). The identity of the compound is confirmed by elemental analysis.

Analysis.-Calcd for C, 38.66; H, 11.9; B, 31.9; N, 8.25. Found: C, 38.62, 38.04; H, 11.90, 11.50; B, 31.01, 31.44; N, 8.22, 8.70.

(C) A reaction vessel is charged with 8 ml. of cyclohexanone and a solution of 0.059 mole of a hydrate of HgBmHm, i.e., (H3O)2B1QH10 in Of 1,2-dimctl1oXyethane and 15 ml. of water. The mixture is stirred a few minutes in an ice bath and the bath is then removed. Stirring is continued at prevailing atmospheric temperature for about 5 minutes and 20 ml. of cyclohexanone is added. The mixture is stirred at about 25 C. for three days to form a red solution.

A portion of the reaction mixture is reacted with ethane 1,2-bis(trimethylphosphonium) diiodide in water to obtain A second portion of the reaction mixture is reacted with an alcohol solution of cesium hydroxide to obtain CS B H OCH CH OCH The compound is a white bygroscopic solid.

Another portion of the reaction mixture is stirred with 300 ml. of isopropyl alcohol containing 40 g. of (CH NOH. The salt is separated by filtration to obtain 5.7 g. of product which is pale violet in color. The salt,

tained as a white crystalline material which is stable in the absence of light but turns dark upon exposure to daylight.

A portion (15.0 g.) of

[( a 4 2 ro a z a s obtained as described in Part A, is dissolved in hot water and the solution is passed through an acidic ion-exchange column of the type described earlier. The acid efiluent which contains H B H OCH CH OCH is titrated with aqueous NaOH solution to a pH value of 7. The neutral solution is evaporatedto dryness to yield NBzBmHgOCHzCHzOCHg as a white crystalline salt.

EXAMPLE 27 An aqueous solution containing 4.0 g. of (NHQ B H is passed through a column packed with an acidic ionexchange resin, described earlier, and the aqueous efiiuent is evaporated under reduced pressure to a volume of 10 ml. This solution of (H O) B H is mixed with 75 ml. of tetrahydrofuran and the mixture is heated on a steam bath for 40 minutes. A blue color forms at first which changes slowly to yellow. The solution is poured with stirring into an aqueous solution of (CH NOH. The white solid which forms is separated by filtration and it is recrystallized from aqueous ethanol to obtain light yellow crystals of bis(tetramethylammonium) butoxynonahydrodecarborate(2-). The identity of the compound is confirmed by elemental analysis.

Analysis.-Calcd for [(CH N] B H O(CH CH t B, 33.4; H, 12.4; C, 40.7. Found: B, 32.75; H, 12.63, 12.20; C, 38.68, 38.46.

Examples 26 and 27 illustrate the compounds of the invention in which X is an OR group. The process of these examples is generic to the preparation of compounds which contain OR" substituents, particularly where R is a hydrocarbon group of an oxygen-interrupted hydrocarbon group of up to 12 carbons. To illustrate, the acid (H O) B H is reacted with methyl ethyl ether to form (H O) B H OC H with methyl octyl ether to form (H O) B H OC H with methyl allyl ether to form (H O) B H OC H with anisole to form 3 )2 10 9 s 5 and with methyl cyclohexyl ether to form The acids can be neutralized with the appropriate bases to form the desired salts, as illustrated in these and other examples.

EXAMPLE 27-A An aqueous solution containing 8.0 g. of (NH B H is passed through a column packed with an acidic ionexchange resin of the type described earlier. The acidic eflluent is evaporated under reduced pressure to a syrup. To this syrup 8 g. of dimethyl disulfide is added and the mixture is stirred at prevailing temperature (about 25 C.) for 24 hours. The mixture is neutralized with aqueous NaOH solution and it is steam-distilled about one hour to remove unreacted CH SSCH The residual solution is evaporated under reduced pressure to a volume of about 25 ml. and aqueous 50% cesium fluoride solution is added in excess. The precipitate which forms is separated and it it recrystallized twice to yield Cs B H (SCH Analysis.-Calcd for Cs B H (SCH C, 5.1; H, 3.0. Found: C, 5.27; H, 3.57.

Example 27-A illustrates compounds of the invention in which X is 4R and a process for obtaining them. The group R' has the meaning defined in the discussion of Examples 26 and 27. Preferably R is an aliphatically saturated hydrocarbon group of at most 12 carbons. The process of Example 27-A is generic to the preparation of compounds having hydrocarbonmercapto groups. It consists simply in reacting an organic disulfide of the formula R"SSR"' with an aqueous solution of the acid H B H also expressed as (H O) B H The substituted compound is most conveniently isolated as an insoluble salt by adding the appropriate cation (M+) to the reaction mixture. However, the reaction mixture can be evaporated to isolate soluble compounds. To illustrate, [(CH N] B H )SC H is obtained from dibutyl disulfide and (CH NCl; (C H NH B H (SC H is obtained from di(2-ethyl'hexyl) disulfide and propyla mine; A12(H20)5]B10I I8(SCH2C6H5)2]3 is Obtained from dibenzyl disulfide and N32B10H9SC12H25 is ob" tained from didodecyl disulfide and odium hydroxide; and CaB H (SC H is obtained from dicyclohexyl disulfide and calcium hydroxide.

EXAMPLE 28 (A) A portion (about 0.5 g.) of CS2B1OH9OH, prepared as described in Example 10, Part A, is dissolved in about 5 ml. of formic acid (98%+) and the solution is heated on a steam bath for 2-3 minutes. It is cooled, diluted with water and a solution of thallium nitrate is added with stirring. The precipitate which forms is separated and washed. The compound, dithallium formyloxynonahydrodecaborate (2), is obtained as a white crystalline material. The identity of the compound, which has the formula Tl B H OC(O)H, is confirmed by its infrared absorption spectrum.

The compound is hydrolyzed to Tl B H OH by reaction with hydrogen peroxide or sodium hydroborate (NaBH (B) The compound CsB H -HC(O)N(CH prepared as described in Example 10, Part A, is dissolved in an aqueous solution of sodium cyanide and the solution is heated on a steam bath for 9-10 minutes. The solution is mixed with an aqueous solution of TlNO and the precipitate which forms is separated to obtain Tl B I-I OC(O)H as a White crystalline solid. The identity of the compound is confirmed by its infrared absorption spectrum.

EXAMPLE 29 (A) A small portion (ca. 0.5 g.) of the hydrate of Cs B H (OH) prepared as described in Example 11, Part C, is dissolved in formic acid (98%+) and the solution is heated on a steam bath for about 3 minutes. The solution is poured into water and aliquot portions of the resulting solution are removed for further reactions, as described below.

One portion is neutralized with aqueous CsOH solution to form the water soluble Cs B H [OC(O)H] A second portion is mixed with aqueous TlNO solution to form the water soluble Tl B I-I [OC(O)H] A third portion is mixed with sufiicient aqueous NaOH solution to make the solution basic. The product,

remains in solution.

An aqueous solution of (C H NOH is added to the remaining reaction mixture and the precipitate which forms is separated to yield The identity of the compound is confirmed by its infrared absorption spectrum.

(B) The process of Part A is repeated employing 1.0 g. of [(CH N] B H (OH) obtained as described in Example 11, Part E, and 6 ml. of glacial formic acid. The mixture is heated on a steam bath for 3 minutes and poured into 25 ml. of propanol. The precipitate is separated and crystallized from aqueous ethanol to obtain the tetramethylammonium salt of the formula shown below.

33 Analysis.-Calcd for [(CH N] B H [OC(O)H] C, 33.8; H, 9.6; B, 30.5. Found: C,30.43, 30.21; H, 9.80, 9.63; \B, 32.63.

EXAMPLE 30 (A) A reaction vessel is charged with 100 ml. of dimethylformamide and an aqueous solution of (about 0.1 mole), obtained as described in Example A, Part C. The solution is heated for one hour on a steam bath and the water is then removed by distillation at atmospheric pressure. The liquid residue is refluxed for 3.5 hours after which it is poured into 200 ml. of methanol which contains in solution 40 g. of

(CH ,NOH 5H O The solution so obtained is stirred into a mixture of 400 ml. of H'CaHqOH and 100 ml. of iso-C H oH. The solid which precipitates is separated by filtration.

The solid is separated into two fractions by repeated crystallization from ethanol and ethanol-water solutions. The less soluble fraction is set aside and it is described further in Example 14, Part A.

The more soluble fraction is dissolved in ethanol-water and l-butanol is added to precipitate a white solid which is bis(tetramethylammonium) formyloxynonahydrodecarborate (2-).

Analysis.Calcd for [(CH N] B H GC(O)I-I: B, 34.8; C, 34.8; H, 11.0; N, 9.0. Found: B, 35.6; C, 34.3; H, 11.5; N, 9.4. p

The above tetramethylammonium salt is dissolved in water and an aqueous solution of TlNO is added with stirring. The solid which forms is separated and crystallized from water to obtain dithallium formyloxynonahydrodecarborate(2-).

Analysis.Calcd for Tl B l-I OC(O)H: T1, 71.6. Found: Tl, 73.2.

B. The process of Part A is repeated employing 100 ml. of HC(O)N(CH and 0.091 mole of dissolved in 23 ml. of water. The mixture is heated and distilled to remove water as described earlier over a period of about 1.5 hours. The reaction mixture is poured into 400 ml. of ethanol containing 30 g. of CsOH. The solid which forms is separated by filtration and it is further separated int-o two fractions by repeated crystallization from 2-propanol-ethanol mixture. The less soluble fraction is set aside and it is described further in EX- ample 14, Part B.

The more soluble fraction is crystallized from water to obtain 16 g. of dicesium monoformyloxynonahydrodecaborate (2-).

Analysis.Calcd for Cs B H OC(O)H: Cs, 62.1; B, 25.0; H, 2.34; C, 2.80. Found: Cs, 62.0; B, 25.57, 25.40; H, 2.65; C, 2.74.

EXAMPLE 31 (A) A reaction vessel is charged with prepared as described in Example 22, Part C, and 65 ml. of Water. The mixture is stirred until a solution is formed and it is then filtered to remove a small quantity of insoluble material. The filtrate is mixed with ml. of

% aqueous hydrogen peroxide solution and the mixture A further quantity of the compound is obtained by pouring the filtrate from the reaction mixture into propanol 34 and separating the precipitate. The identity of the compound is confirmed by its infrared absorption spectrum and by elemental analysis.

Analysis.-Calcd for [(CH N] B H OC(O)C H B, 28.0; C, 46.0; H, 9.85; N, 7.25. Found: B, 27.83, 27.58; C, 46.96, 46.90; H, 10.03, 10.04; N, 7.20, 7.40.

(B) The product of Part A is stable in boiling water and it forms a thallium salt of the formula by reaction in aqueous solution with TlNO The thallium salt is a white crystalline compound which is insoluble in water.

(C) The produce of Part A is hydrolyzed by refluxing 2 hours in 10 m1. of 20% NaOH and the resulting solution is reacted with aqueous TlNO to form Tl B H OH, a compound also obtained in Example 10, Parts C and D.

(D) The product of Part A is dissolved in hot water and the solution is passed through an acidic ion-exchange column of the type described previously. The acidic efiiuent, which contains H B H OC(O)C H is titrated with aqueous NaOH solution until neutral. The neutral solution is evaporated to dryness to yield disodium benzoyloxynonahydrodecaborate(2-), i.e., Na B l-I OC(O)C H as a white crystalline hygroscopic salt.

Example 31 illustrates the compounds of the invention in which X is hydrocarbonyloxy, i.e., -OC(O)R, where R has the meaning given earlier in the specification. The process of Example 31 is generic for the preparation of esters. The most versatile and, therefore, preferred method is the reaction of decaborate salts having hydroxyl groups with an organic acid. To illustrate, CS B H OH can be reacted (1) with propionic acid to obtain Cs B H OC(O)C H (2) with methacrylic acid to obtain Cs B H OC(O)C(CH ):CH

(3) with dodecanoic acid to obtain and (4) with toluic acid to obtain Cs B H OC(O C H CH In like manner (NH B H (OH) can be reacted (1) with hexahydrobenzoic acid to yield 4)a io sl s nlz (2) with trichloroacetic acid to yield i)2 1o s[ 3]2 (3) with trifiuoroacetic acid to yield and (4) with naphthoic acid to yield i)2 10 8[ 1O 7]2 The process of Examples 2831 can be used to prepare compounds of the invention in which X is caroamoylpxy,

where R is an organic group as defined earlier. In this manner of operation decaborates having -OH groups as substituents are reacted with carbamyl chlorides, e.g.,

trate, Na B H OI-I can be reacted (l) with NH C(O)Cl to'obtain Na B H OC(O)NI-l (2) with (CH NC(O)Cl to yield Na B H OC(O)N(CH and (3) with C H NHC(O)Cl to yield Na B H OC(O)NHC H Further, by way of illustration, (NH B H (OH) can be reacted (1) with An aqueous solution of benzenediazonium chloride (13.8 millimoles) is added at C. to 2.0 g. of diammonium decahydrodecaborate(2-) in 50 ml. of water. A brown solid precipitates which explodes readily when dry. The solid dissolves in ethanol at steam bath temperatures to form a deep red solution which is useful for dyeing wool and viscose rayon fibers a red color. Evaporation of the alcohol yields a solid which is extracted with hot benzene. The residual solid is brown and non-explosive. It is shown by infrared analysis to be a decaborate salt having a phenylazo group on the decaborate anion.

The above example illustrates a compound of the invention in which the group X is -N=N-aryl. By employing the appropriate diazonium chloride compounds of the invention can be obtained in which X is tolylazo, naphthylazo, chlorophenylazo, and the like.

The examples which follow illustrate compounds of the invention which have a plurality of X groups in which the X groups are not alike.

EXAMPLE 33 (A) A reaction vessel is charged with 4.6- g. of [(CH3)4NJZBIOHQOCH2CHZOCH3, obtained as described in Example 6, Part A, and 75 ml. of CH CN. Chlorine gas is passed into the suspension and the temperature rises to 70 C. The suspended solid dissolves rapidly and the solution becomes reddish brown. Passage of chlorine is continued for about one hour until the temperature drops to about 30 C. The solution is evaporated under reduced pressure and the residue is stirred with water. Aqueous (CH NOH is added and the mixture is heated to boiling. The solution is filtered, the filtrate is cooled and the crystals which form are separated. The product is crystallized from water to obtain bis(tetramethylamrnonium)nonachloromono(2 methoxyethoxy)decaborate- (2"), i.e., 2B1oCl9OCH cH2OCH3- (B) A mixture is prepared consisting of 14.4 g. of [(CH N] B H OCH CH OCH and 150 ml. of anhydrous CH CN. The mixture is stirred and chlorine gas is passed through it, using ice-bath cooling as needed, to maintain the temperature at 20-25 C. After passage of chlorine for one hour the reaction mixture is a clear dark-colored solution. The mixture is evaporated to obtain a thick syrup which is stirred into an aqueous solution of (CH NCI. A precipitate forms which is separated and recrystallized from aqueous ethanol to obtain [(CH N] B Cl OCH CH OCH as a white crystalline product. The identity of the compound is confirmed by elemental analysis.

Analysis.Calcd for B, 16.6; C, 20.3; H, 4.8; CI, 49.0; N, 4.3. Found: B, 17.0; C, 18.9; H, 4.8; Cl, 53.0; N, 4.3.

EXAMPLE 34 tity of the compound is confirmed by elemental analysis.

Analysis.Calcd for B, 10.3; Br, 68.4; C, 12.4; H, 2.94. Found: B, 10.03; Br, 67.99; C, 12.40, 12.76; H, 3.24, 3.39.

(B) A reaction vessel is charged with 180 ml. of methanol, 60 ml. of water and 6.2 g. of

The mixture is stirred until the solid dissolves and a solution of 36 g. of bromine in 120 ml. of methanol is added slowly and with stirring over a period of 2 hours. Tetramethylammonium hydroxide is added until the color of excess bromine is gone and then 5 g. more of the base is added. A solid forms which is separated and washed with 50 ml. of water. The filtrate is diluted with 50 ml. of Water and it is distilled until the methanol is removed. The solid which separates is removed by filtration and combined with the previous solid. The combined solids are washed with water to obtain 16.1 g. of product which is [(CH3)4NJ2BIUBI'QOCHZCH2OCH3.

(C) The product of Part A is dissolved in hot water and the hot solution is passed through an acidic ion-exchange resin of the type described earlier. The aqueous efiiuent, which contains H B Br OCH CH OCH is titrated with aqueous NaOH solution to a pH value of 7. The neutral solution is evaporated to dryness to obtain Na B Br OCH CH OCH containing water of hydration. The product is a white crystalline solid.

(D) A solution of the acid H B Br OCH CH OCH prepared as described in Part C, is stirred with an aqueous solution of silver nitrate for 15 minutes. The precipitate which forms is separated, washed and dried to obtain AgzB gBl'gocHzcHzocHg.

Analysis.-Calcd for the above formula: C, 3.22; H, 0.63; B, 9.68. Found: C, 3.11; H, 0.92; B, 9.90.

EXAMPLE 35 (A) A glass reaction vessel is charged with 30 g. of (NH4)2B1QH1D and of (CH3)2SO. The mixture is stirred until a clear solution is formed and anhydrous HCl is bubbled into the mixture with continued stirring. An exothermic reaction sets in and the vessel is immersed in an ice bath to maintain the temperature below 45 C. A large quantity of NH Cl forms as a precipitate and the solution is filtered to separate the solid. The filtrate is returned to the reaction vessel and the passage of HCl is continued until the reaction is no longer exothermic. The mixture is filtered again and the filtrate is diluted with water. A sticky mass forms which is separated by decantation of the water. The mass is triturated alternately with water and with acetone to separate the portions which are soluble in each of these liquids. The acetone extract is diluted with water and the solid which precipitates is separated by filtration. The solid is purified by repeated solution in acetone and precipitation with water and, finally, crystallization from acetone-water solution. The solid so obtained, which is B H -2S(CH melts at 265-266 C. It is employed as a reactant in the next step of the process.

Analysis.-Calcd for B H -2S(CH B, 45.0; C, 19.98; H, 8.39; S, 26.62. Found: B, 44.69; C, 19.56; H, 8.32; S, 27.19.

A reaction vessel is charged with 7.0 g. of

and ml. of acetonitrile. The mixture is stirred and chlorine gas is bubbled through it at a moderate rate. The temperature of the solution rises to about 65 C. and it is maintained at this point by the heat of the reaction for about one hour. At this time the temperature begins to drop and heat is applied to maintain the reaction at reflux temperature for one hour with continued passage of chlorine gas. The solution is cooled to about 25 C. and it is poured into 500 ml. of water with stirring.

37 A heavy oil forms from which the supernatant liquid is separated by filtration. The solid is washed with ethanol and dried to obtain 8.0 g. of bis(dimethylsulfide)hexachlorodihydrodecaborane (8) Analysis.Calcd for B H Cl -2S(CH B, 24.2; C, 10.72; H, 3.14; Cl, 47.6; S, 14.3. Found: B, 24.43; C, 10.83, 10.92; H, 3.41; Cl, 45.15; S, 14.85.

The product, so obtained, is employed as a reactant in the next step of the process.

A reaction vessel is charged with 1.0 g. of

and 8 ml. of (C H P. The mixture is allowed to stand overnight (18-24 hours) at about 25 C. and it is then heated to 195 C. under a nitrogen atmosphere for about 20 minutes. The mixture is cooled, benzene is added and the mixture is stirred thoroughly. The insoluble portion is separated by filtration and it is dissolved in methanol. A methanol solution of (CH NCl is added with stirring to form an insoluble salt which is separated. The product is bis(tetramethylammonium) hexachlorodi(methylthio) dihydrodecaborate(2-) Whose identity is confirmed by elemental analysis.

Analysis.-Calcd for [(CH N] B H CI (SCH B, 19.1; S, 11.3; N, 4.96. Found: B, 18.78; S, 11.31; N, 4.26.

(B) A reaction vessel is charged with 2.0 g. of B I-I Cl '2S(CH and 15 ml. of (C H P. The mixture is heated to 135 C. under a blanket of nitrogen. The mixture becomes an oil and it is cooled to about 25 C. It is processed as described in the last paragraph of Part A. There is obtained 2.0 g. of [(CH N] B H Cl (SCH EXAMPLE 36' (A) A reaction vessel is charged with 4.0 g. of [(CH N] B H C(O)C H and 60 ml. of acetonitrile. The solution is cooled in an ice bath and chlorine gas is passed through it for about one hour. The bath is removed and passage of chlorine gas is continued for another hur at prevailing atmospheric temperature (about 25 C.). After passage of chlorine gas is stopped the solution is warmed under reduced pressure to remove the acetonitrile. A brittle glassy solid remains of which a portion is crystallized twice from aqueous ethanol to obtain 3.1 g. of his (tetramethylammonium) monobenzoylnonachlorodecaborate(2'). The identity of the com-pound is confirmed by elemental analysis.

Analysis.Calcd for [(CH N] B Cl C(O)C H C, 26.4; H, 4.29; N, 4.1; B, 15.85; Cl, 46.9. Found: C, 25.13, 24.71 H, 4.47, 4.54; N, 4.33, 4.47; B, 16.08; Cl, 48.1.

(B) The reaction of Part A is repeated, employing 7.5 g. of [(CI-I N] B H C(O)C H and 175 ml. of CH CN. The reaction slurry is cooled and chlorine gas is passed into it at a rate to maintain the temperature at 30-35 C. A clear dark red solution forms. This solution is evaporated under reduced pressure to about one-third its original volume and the liquid is poured into ethanol. The precipitate is processed as described in Part A to obtain 12 g. of [(CH N] B Cl C(O)C l-I The elemental analysis is as follows: C, 25.9, 25.69; H, 4.62, 4.69; B, 15.85, 15.77; Cl, 46.9, 45.78. I

(C) A column is packed with an acidic ion-exchange resin of the type described earlier and the resin is converted to the sodium salt by passing an aqueous solution of NaOH through it. The resin is washed until the effluent is neutral and the column is then flushed with aqueous ethanol (1:1). A solution of 7.3 g. of

in about 400 ml. of water is passed through the column and the efiiuent is evaporated to dryness under reduced pressure. The sodium salt, Na B Cl C(O)C I-I is obtained as a very hard, glass-like, hydroscopic solid.

An aqueous solution of the sodium salt is mixed with 38 aqueous cesium fluoride to precipitate the cesium salt. The precipitate is separated and dried to yield 5 g. of crystalline CS B Cl C(O)C H EXAMPLE 37 A solution Of of [(CH N] B H C(O)C H in about 300 -ml. of water is passed through a column packed with an acidic ion-exchange resin, as described earlier. The column is washed with water until the effluent forms no precipitate with aqueous AgNO The efiiuent is evaporated under reduced pressure to a volume of about 400 ml. The solution, which contains (H O) B H C(O)C H is cooled in an ice-bath and chlorine gas in bubbled through it at a moderate rate for 3 hours. The ice-bath is removed and passage of chlorine gas is continued for 4 hours. The temperature of the solution rises to a maximum of 40 C. and then drops slowly. Passage of chlorine is stopped and one'half (200 ml.) of the solution is used for further processing.

A soluiion of 20 g. of CsF in 50 -ml. of water is added to the portion (200 ml.) of the reaction mixture and the solution is cooled to about 10 C. The white solid which forms is separated by filtration and it is crystallized from water to Obtain CS2B1QC19C(O)C5H3C12'H2O. The of the compound is confirmed by elemental analysis.

Analysis.-Calcd for C'S2B10H5C7Clu0zi CS, H, 0.56; B, 12.19; Cl, 44.0. Found: Cs, 29.2; H, 0.79; B, 12.16; Cl, 44.09.

EXAMPLE 38 (A) A reaction vessel is charged with a solution consisting of 10 ml. of water, 10 ml. of methanol and 0.5 g. of [(CH N] B H C(O)C H The solution is cooled in an ice bath and a solution of 2.5 ml. of bro-mine in 10 ml. of methanol is added with agitation. An exothermic reaction develops and the temperature is maintained below about 40 C. by cooling. The bromine is absorbed rapidly in the first stage of the reaction but a slight excess of bromine remains at the end of the addition. The solution is filtered and the filtrate is chilled in liquid nitrogen until a large amount of solid precipitates. The solid is separated by cold filtration and it is crystallized from boiling water to give a small quantity of gray-White crystals of his (tetrarnethylammonium) nonabromomonobenzoyldecaborate (2), [(CH N] B Br C(O)C H The identity of the compound is confirmed by elemental analysis.

Analysis.-Calcd for [(CH N] B Br C(O)C l-I C, 16.65; H, 2.68; B, 10.0; Br, 66.6. Found: C, 16.62, 16.59; H, 3.19, 3.01; B, 10.07; Br, 68.34.

(B) A reaction vessel is charged with 50 ml. of acetonitrile and 6.0 g. of [(CH N] B H C(O)C H The mixture is stirred to dissolve as much of the decaborate salt as possible. A further quantity ml.) of acetonitrile is added and the mixture is stirred again for a short period. It is filtered, the filtrate is returned to the reaction vessel and 1.4- g. of

isadded with 100 ml. of acetonitrile. The mixture is stirred again and 50 ml. of CH OH is added to facilitate the solution of the last portion of the decaborate salt. The clear solution is cooled in an ice-bath and a solution of 30 ml. of bromine in acetonitrile is added in portions with vigorous stirring. After about one-half of the bromine solution is added, the ice-bath is removed and the remaining bromine solution is added slowly. Excess bromine is present in the solution after addition is completed and the solution is stirred for 2 hours at prevailing atmospheric temperature. It is then evaporated at about 100 C. under reduced pressure, and the residue is mixed with 250 ml. of water. A gum forms which is separated by filtration and crystallized from aqueous ethanol to obtain 5.4 of [(CH3)4N]2B1OBIQC(O)CGH5.

Analysis.-Calcd for [(CH N] B Br C(O)C H B, 10.0; C, 16.65; H, 2.68; Br, 66.0. Found: B, 9.87; C, 16.55; H, 3.06; Br, 66.0.

A portion (485 g.) of the tetramethylammonium salt, obtained above, is dissolved in boiling water and the solution is passed through a column packed with an acidic ion-exchange resin of the type described in Example A, Part C. The efiluent, which is clear, colorless and acidic, contains H B Br C(O)C H It is titrated to the neutral point with 0.1 N NaOH. The neutral solution is evaporated under reduced pressure and dried to yield Na B Br C(O)C H as a brittle solid.

EXAMPLE 39 A quantity Of I:(CH3)4NJQB1OCIQC(O)C5H5, prepared as described in Example 36, Part A, is dissolved in boiling water and the hot solution is passed through a column packed with an acidic ion-exchange resin of the type described earlier. The acid efliuent, which contains H B C1 C(O)C H is evaporated under reduced pressure to a volume of about 100 ml. and it is neutralized with aqueous sodium hydroxide solution to a pH of 10. It is again evaporated to a volume of ml. and the concentrated solution is added with stirring to 20 ml. of an aqueous solution containing 3 g. of sodium acetate and 2 g. of the hydrochloride of semicarbazide. The solution is heated on a steam bath for 2 hours.

A portion of the solution is mixed with aqueous (CH NOH and the solid which forms is separated to obtain the semicarbazone, as the tetramethylammonium Salt, 1.3-,

A second portion of the solution is mixed with an aqueous solution of (CH SI and the solid which forms is separated to obtain the semicarbazone as a trimethylsulfonium salt.

Analysis.Calcd for B, 14.5; C, 22.6; H, 3.5; N, 5.65; Cl, 43.0. Found: B, 15.05; C, 21.7; H, 3.37; N, 4.56; Cl, 44.66.

EXAMPLE 40 One-half of the solution obtained in the first phase of the reaction in Example 11, Part F, is acidified with aqueous hydrochloric acid and chlorine gas is passed through the solution until the exothermic reaction subsides and the temperature drops to about 25 C. The liquid, which contains a small quantity of solid, is passed through an acidic ion-exchange resin and the acid efiiuent is diluted to a volume of 400 ml. with water. Chlorine gas is passed through the acid solution for about 3 hours. The temperature rises to 52 C. initially and stays at about 50 C. The solution is filtered and the filtrate, which contains H B CI OH, is mixed with an aqueous solution of (CH NCl to precipitate The compound is separated by filtration and it is crystal- EXAMPLE 41 (A) A reaction vessel is charged with 20.5 g. of his (N-methy1-2-pyrrolidone) octahydrodecaborane (8), prepared as described in Example 11, Part A, 100 ml. of water and 7 g. of NaOI-I. The mixture is refluxed for 2 hours and about one-fourth of the solution is removed for reaction as described in Part B which follows.

(B) The portion of the solution obtained in Part A is acidified with aqueous hydrochloric acid at about 25 C. and chlorine gas is passed into the solution. The temperature rises spontaneously to 96 in about 10 minutes and thereafter it drops slowly until, after about 2 hours it reaches 50 C. Heat is then applied to maintain the tem perature at 50 C. and passage of chlorine gas is continued for 30 minutes. Passage of chlorine gas is stopped and water is added to the solution in sufiicient quantity to dissolve any solid which forms. A concentrated solution of 10 g. of (CH NOH is added with stirring and the precipitate which forms is separated. The solid is crystallized from water to obtain 2.3 g. of bis(tetramethylammonium) octachlorodihydroxydecaborate(2"). The identity of the white crystalline compound is confirmed by elemental analysis.

Analysis.Calcd for [(CH3)4N]2B10C13(OH)2: B, 18.8; C, 16.8; H, 4.5; Cl, 49.4; N, 4.8. Found: B, 19.11, 19.38; C, 17.15, 17.18; H, 4.90, 4.94; Cl, 49.29, 49.55; N, 3.70, 3.63.

(C) The remaining portion of the solution obtained in Part A is employed to prepare a further quantity of [(CH3)4N]2B1 C1g(OH)2, as described in Part B. An aqueous solution of this salt is passed through a column packed with an acidic ion-exchange resin of the type described earlier. The acid efiluent is evaporated until a viscous liquid remains. On standing the liquid crystallizes to yield a hydrate of the free acid H B Cl (OH) Analysis.Calcd for H B Clg(OH) -9H O: B, 18.3; C1, 48.1. Found: B, 18.63; Cl, 48.80.

EXAMPLE 42 (A) A solution of 0.58 g. of diammonium decahydrodecaborate (2-) in 50 ml. of water is chilled in an icewater bath to about 0 C. To the cooled solution there is added carefully and with stirring an aqueous solution prepared at 0 C. fro-m 0:26 g. of sodium nitrite and 0.4 g. of concentrated hydrochloric acid. The solution is stirred and allowed to warm to room temperature. Chlorine is then passed through at a moderate rate. The temperature rises spontaneously to 33 C. and the addition of chlorine is continued until the temperature falls back to about 25 C. A solution of 3 g. of cesium chloride in 4 ml. of water is then added. Filu'ation gives 0.2 .g. of a cesium salt of a chlorinated decaborate(2-) bearing substituents which have nitrogen-oxygen bonds. The compound is a dark brown solid whose elemental analyses suggest the product is CsHB HCl-1(NO) Analysis.-C-alcd for B Cl CsH Ngo z B, 19.6; C1, 45. 1; Cs, 24.0; H, 0.36; N, 5.08. Found: B, 20.7; C1, 44.6; Cs, 23.6; H, 0.66; N, 5.97, 5.63.

(B) The filtrate from the above separation is a dark blue liquid. Aqueous tetramethylammonium chloride solution is added to this filtrate until precipitation of a blue solid is completed. The solid, which is separated by filtration, is purified by solution in acetone and reprecipitation by the addition of ethanol to the acetone solution. The blue solid, which has a k,,,,,, of 1.98 at 583 my. and of 0.69 at 440 mg, is bis(tetramethylammonium) nonachloronitrodecaborate(2), [(CH N] B Cl NO The identity of the compound is confirmed by elemental analysis.

Analysis.--Calc-d for C H B Cl N O C, 15.5; H, 3.88; B, 17.35; Cl, 5 1.4; N, 6.78. Found: C, 13.66; H, 3.93; B, 17.37; Cl, 49.65; N, 5.07.

(C) Bis(tetrame'thylammonium) nonachloronitrodecaborate(2) is converted to its parent acid by stirring in acetone with a strongly acid ion-exchange resin such as Amberlite IR (acid form) followed by filtration and removal of the solvent by evaporation. The parent acid, i.e., (H O) B Cl NO thus obtained is a viscous blue liquid which is converted to its cesium salt (CS B CI NO by reaction in concentrated aqueous solution with cesium chloride.

EXAMPLE 43- (A) A solution containing 0.5 g. of bis(tert.-butylammonium) decahydrodecaborate(-2-),

in 20 ml. of water is chilled to 0 C. in ice-water. To this cooled solution, there is added carefully and with vigorous 

1. A COMPOUND OF THE FORMULA MA(B10H10-YXY)B WHEREIN M IS A CATION HAVING THE PROPERTY OF FORMING A POSTIVELY CAHRGED GROUP IN WATER; X IS A MONOVALENT GROUP WHICH HAS THE CHARACTERIZING PROPERTY OF FORMING X-C BONDS WHEN C REPRESENTS A CARBON WHICH IS A NUCLEAR MEMBER OF A BENZENE RING AND WHERE THE X-C BOND IS FORMED IN PLACE OF THE H-C BOND AND WHEN MORE THAN ONE X GROUP IS PRESENT THE XS CAN BE DIFFERENT; Y IS A POSITIVE WHOLE NUMBER OF 1 THROUGH 10, INCLUSIVE; AND A AND B ARE POSITIVE WHOLE NUMBERS OF 1 THROUGH 3, INCLUSIVE AND A MULTIPLIED BY THE VALENCE OF M IS EQUAL TO 2B. 